CN109996781A - Using zeolite catalyst by the ethylene glycol reforming method for ethylenediamine - Google Patents

Using zeolite catalyst by the ethylene glycol reforming method for ethylenediamine Download PDF

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CN109996781A
CN109996781A CN201780070277.3A CN201780070277A CN109996781A CN 109996781 A CN109996781 A CN 109996781A CN 201780070277 A CN201780070277 A CN 201780070277A CN 109996781 A CN109996781 A CN 109996781A
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zeolitic material
preferable
mixture
catalyst
weight
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A-N·帕伏列斯库
A·戈迪略
M·K·施勒特尔
J-P·梅尔德
J·贝克特尔
T·海德曼
S·顺克
U·米勒
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
    • C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B01J29/185—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/26—Mordenite type
    • C01B39/265—Mordenite type using at least one organic template directing agent
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/09—Diamines
    • C07C211/10—Diaminoethanes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/14—Amines containing amino groups bound to at least two aminoalkyl groups, e.g. diethylenetriamines

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

Ethane -1,2- diamines and/or H are converted by ethane -1,2- glycol the present invention relates to a kind of2N‑[CH2CH2NH]n‑CH2CH2NH2L-PEI method, wherein n >=1, which comprises (i) is provided comprising containing YO2And X2O3Zeolitic material catalyst, wherein Y be quadrivalent element, X is triad, wherein the zeolitic material be selected from MOR, FAU, CHA and/or GME skeleton structure zeolitic material, combination of two or more including it；(ii) gas streams comprising the pure and mild ammonia of ethane -1,2- two are provided；(iii) contact the catalyst provided in (i) with the gas streams provided in (ii), to convert ethane -1,2- diamines and/or L-PEI for ethane -1,2- glycol.

Description

Using zeolite catalyst by the ethylene glycol reforming method for ethylenediamine
Technical field
Ethane -1,2- diamines and/or formula H are converted by ethane -1,2- glycol the present invention relates to a kind of2N- [CH2CH2NH]n-CH2CH2NH2L-PEI method, wherein n >=1, the method use is comprising containing YO2And X2O3 Zeolitic material catalyst, wherein Y be quadrivalent element, X is triad, wherein the zeolitic material be selected from MOR, The zeolitic material of FAU, CHA and/or GME skeleton structure.
Background technique
Introduction
Modenite (MOR) is a kind of channel 8MR (side pocket (side with 1 the dimension 12 member rings channel (MR) and intersection Pockets large pore zeolite)).Al, which is substituted onto, to be produced in neutral silicate framework by the charge unbalance (example of cation compensation Such as, the O-H group of Bronsted acid is served as).The zeolite of these classifications is previously described for various types of chemistry Conversion, such as the reaction of Friedel-Crafts type, isomerization, carbonylation (carbonilation) and amination method.It also describes It is synthesized according to the MOR zeolite of differential responses approach, such as without templated synthesis (in the case where organic pore former is not present), template Synthesis or rear modification such as dealumination reaction.Therefore, WO 2014/135662A is related to being melted into dimethyl ether (DME) carbonyl with synthesis gas Methyl acetate, used in MOR zeolite preferably use tetraethylammonium bromide (TEABr) template prepare.US 7,605,295 is related to Using the transalkylation method of small crystals MOR zeolite, the Average crystallite length that the zeolite is parallel to the hole 12MR direction is preferably 50nm, wherein the zeolite is prepared with TEABr template.Similarly, 7 US, 687,423B2 are related to having the micro- of MOR framework structure Brilliant synthesis also relates to wherein there is the crystallite 60nm or smaller to be parallel to the Average crystallite length in 12 ring channels directions And their purposes in the transalkylation of aromatic compounds.Grundner, Sebastian etc. are in Nat.Commun.2015, and Volume 6, as methane oxidation at selectivity/active catalyst Cu-MOR of methanol involved in document number 7546, including from Cu (OAc)2Starting is without the specific Cu ion-exchange process of continuous calcining.
It it is known that Gas-Phase Amination of the catalyst based on modenite for by being mainly monoethanolamine synthesizes ethylidene Amine.Therefore, 4 US, 918,233 report purposes of the rear-earth-doped MOR for monoethanolamine (MEOA) Gas-Phase Amination, wherein It is 80% to the selectivity of EDA under 26%MEOA conversion ratio.CN 1962058A is related to using comprising combining with Zn or Fe The mordenite catalyst of one of Zr, Nb, Mo or Sn carry out amination ethanol amine with gas phase synthesis of ethylenediamine.JP H0687797A and JP H07247245A relates separately to the method using dealuminium mordenite catalyst by ammonia and monoethanolamine gas phase reaction at ethylenediamine. CN 101215239 is also described with P modified mordenite, is used to prepare EDA and bridged piperazine derivatives by MEOA.
B.CN 101406845A describes a kind of H- modenite amination catalysis and its preparation.CN 102974393A is related to And a kind of regeneration method of modified zeolite molecular sieve amination catalysis.CN 103007984A, which is claimed, a kind of to be prepared amination and urges The method of agent.CN 102233272A and CN 102190588A are disclosed through Study on Catalytic Amination of Alcohols monoethylene glycol (MEG) and are prepared The method of EDA.
In addition, thesis " Heterogeneous Transition Metal Catalyzed Amination of Aliphatic Diols ", Achim Fischer, Diss.ETH No 12978,1998 is discussed list Ethylene glycol and monoethanolamine are separately converted to the zeolite catalysis method of ethylenediamine.WO 2009/083580A1 is related to a kind of using base It is used as catalyst by ethylene oxide, ethylene glycol or ethanol amine in fluoropolymer-copolymer (Nafion) of sulfonated tertafluorethylene The amination method for preparing ethylene amines.US 4918233 is related to using dealuminium mordenite catalyst by monoethanolamine and ammonia system Standby ethylenediamine.It should be pointed out that all above methods are directed to implement in the liquid phase and need the amination method using high pressure.
Finally, CN 101215239A is related to the joint preparation of ethylenediamine and aminoethylpiperazine, wherein the method includes Use the mordenite catalyst of P Modification.
Despite the presence of the method that can be used for monoethylene glycol amination, it is still desirable to provide the improved method for using catalyst, institute It states catalyst and not only shows higher activity, but also allow to improve the selectivity to aminate, especially to ethylenediamine Selectivity.
Summary of the invention
Detailed description
Ethane -1,2- diamines and/or formula are converted by ethane -1,2- glycol therefore, the purpose of the present invention is to provide a kind of H2N-[CH2CH2NH]n-CH2CH2NH2L-PEI method, wherein n >=1, this allows in higher monoethylene glycol Ethane -1,2- the diamines and/or formula H of more high yield are obtained under the conversion ratio of precursor compound2N-[CH2CH2NH]n-CH2CH2NH2 L-PEI, wherein n >=1.It has therefore been surprisingly found that by using comprising with MOR, FAU, CHA and/ Or the catalyst of the zeolitic material of GME skeleton structure, it include the zeolitic material with MOR framework structure especially by using Catalyst provides and a kind of converts ethane -1,2- diamines and/or formula H for ethane -1,2- glycol2N-[CH2CH2NH]n- CH2CH2NH2L-PEI (wherein n >=1) method, not only allow for obtaining higher conversion ratio, and furthermore It is more selective to ethane -1,2- diamines and/or above-mentioned L-PEI.
Therefore, ethane -1,2- diamines and/or formula H are converted by ethane -1,2- glycol the present invention relates to a kind of2N- [CH2CH2NH]n-CH2CH2NH2L-PEI method, wherein n >=1, which comprises
(i) it provides comprising containing YO2And X2O3Zeolitic material catalyst, wherein Y be quadrivalent element, X is triad, Wherein the zeolitic material is selected from the zeolitic material with MOR, FAU, CHA and/or GME skeleton structure, including its two kinds or more A variety of combinations；
(ii) gas streams comprising the pure and mild ammonia of ethane -1,2- two are provided；
(iii) contact the catalyst provided in (i) with the gas streams provided in (ii), thus by ethane -1,2- bis- Alcohol is converted into ethane -1,2- diamines and/or L-PEI,
Wherein n is preferably 1-8, more preferably 1-5, more preferably 1-4, more preferably 1-3, more preferably 1-2, wherein more It is preferred that n=1.
, it is preferred according to the present invention that including in (ii) middle gas streams for providing and being contacted in (iii) with catalyst In an amount of from 0.1-10 volume %, preferably 0.5-5 volume %, more preferable 1-4.5 volume %, more preferable 1.5-4 volume %, more preferably 2-3.7 volume %, more preferable 2.5-3.5 volume %, ethane -1,2- glycol of more preferable 2.7-3.3 volume %.It is particularly preferred It is that offer and the gas streams contacted in (iii) with catalyst include the second in an amount of from 2.9-3.1 volume % in (ii) Alkane -1,2- glycol.
According to the present invention, to the amount of the ammonia in the gas streams for providing in (ii) and being contacted in (iii) with catalyst It is not particularly limited.Thus, for example, may include in (ii) middle gas streams for providing and being contacted in (iii) with catalyst In an amount of from 5-90 volume %, preferably 10-80 volume %, more preferable 20-70 volume %, more preferable 25-60 volume %, more preferably 30-50 volume %, more preferable 35-45 volume %, the ammonia of more preferable 37-43 volume %.However, particularly preferred according to the present invention It is that offer and the gas streams contacted in (iii) with catalyst include the ammonia in an amount of from 39-41 volume % in (ii).
About the ammonia in the gas streams for providing in (ii) and being contacted in (iii) with catalyst: ethane -1,2- glycol Molar ratio is not particularly limited, so that any conceivable ammonia may be selected: ethane -1,2- glycol molar ratio is implemented Method of the invention.Thus, for example, the ammonia in (ii) middle gas streams for providing and being contacted in (iii) with catalyst: second Alkane -1,2- glycol molar ratio can be 1-45, preferably 2-35, more preferably 4-30, more preferably 6-25, more preferably 8-20, More preferably 10-16.However, according to the present invention it is particularly preferred that providing in (ii) and being contacted in (iii) with catalyst Gas streams in ammonia: ethane -1,2- glycol molar ratio be 12-14.
According to the present invention, in principle in the gas streams for providing in (ii) and being contacted in (iii) with catalyst There is no limit for the content of hydrogen.Thus, for example, providing in (ii) and the gas streams contacted in (iii) with catalyst can It further includes in an amount of from 0.1-70 volume %, preferably 0.5-50 volume %, more preferable 1-40 volume %, more preferable 5-35 body Product %, more preferable 10-30 volume %, more preferable 15-25 volume %, the hydrogen of more preferable 17-23 volume %.However, according to this Invention is it is particularly preferred that offer and the gas streams contacted in (iii) with catalyst include in an amount of from 19-21 in (ii) The hydrogen of volume %.
Alternatively, for example, may include 1 volume % in (ii) middle gas streams for providing and being contacted in (iii) with catalyst Or less, preferably 0.5 volume % or less, more preferable 0.1 volume % or less, more preferable 0.05 volume % or less are more excellent Select 0.001 volume % or less, more preferable 0.0005 volume % or less hydrogen.However, particularly preferred according to the present invention It is that offer and the gas streams contacted in (iii) with catalyst include 0.0001 volume % or less hydrogen in (ii).
, it is preferred according to the present invention that providing in (ii) and gas streams for contacting in (iii) with catalyst are into one Step includes in an amount of from 5-90 volume %, preferably 10-80 volume %, more preferable 20-70 volume %, more preferable 25-60 volume %, more It is preferred that 30-50 volume %, more preferable 35-45 volume %, the inert gas of more preferable 37-43 volume %.According to the present invention especially Preferably, it is provided in (ii) and the gas streams contacted in (iii) with catalyst is further included in an amount of from 39-41 body The inert gas of product %.
The type that can be used for the inert gas of the method for the present invention is not particularly limited, condition be under the conditions of selected, Ethane -1,2- glycol is allowed to be converted into ethane -1,2- diamines and/or formula H2N-[CH2CH2NH]n-CH2CH2NH2Linear poly- second Alkene imines, wherein n >=1.Thus, for example, inert gas may include one or more gases selected from such as the following group: rare gas, N2And its mixture of two or more, it is preferably selected from He, Ne, Ar, N2And its mixture of two or more, wherein more It is preferred that inert gas includes Ar and/or N2, preferably N2.It is particularly preferred, however, that inert gas is Ar and/or N2, preferably N2。
According to the present invention, in principle in the gas streams for providing in (ii) and being contacted in (iii) with catalyst There is no limit condition is H to water content2O content is 5 volume % or less.Thus, for example, being provided in (ii) and in (iii) The gas streams contacted with catalyst may include in an amount of from 3 volume % or less, preferably 1 volume % or less, more preferable 0.5 body Product % or less, more preferable 0.1 volume % or less, more preferable 0.05 volume % or less, more preferable 0.01 volume % or more It is few, more preferable 0.005 volume % or less, more preferable 0.001 volume % or less, more preferable 0.0005 volume % or less H2O.However, according to the present invention it is particularly preferred that the gas streams for providing in (ii) and being contacted in (iii) with catalyst It is preferably not aqueous comprising 0.0001 volume % or less water.
, according to the invention it is preferred to which the gas streams provided in (ii) are heated before being contacted in (iii) with catalyst. Thus, for example, 120-600 DEG C, preferably 150-550 DEG C, more preferable 180-500 can be heated to the gas streams that provided in (ii) DEG C, more preferable 200-450 DEG C, more preferable 230-400 DEG C, more preferable 250-370 DEG C, more preferable 270-350 DEG C, more preferable 280- Then 320 DEG C of temperature is contacted with catalyst at such a temperature in (iii).However, it is particularly preferred to by being mentioned in (ii) The gas streams of confession are heated to 290-310 DEG C of temperature, then contact at such a temperature with catalyst in (iii).
According to the present invention, there is no limit as long as second for the condition contacted with gas streams to catalyst in (iii) in principle Alkane -1,2- glycol is converted into ethane -1,2- diamines and/or formula H2N-[CH2CH2NH]n-CH2CH2NH2L-PEI, Wherein n >=1.Thus, for example, contact of the catalyst in (iii) with gas streams can be in 0.05-20MPa, preferably 0.1- 10MPa, more preferable 0.3-5MPa, more preferable 0.5-3MPa, more preferable 0.6-2MPa, more preferable 0.7-1.5MPa, more preferably It is carried out under the pressure of 0.8-1.3MPa.However, according to the present invention it is particularly preferred that catalyst in (iii) with gas streams Contact carried out under the pressure of 0.9-1.1MPa.
About the gas hourly space velocity (GHSV) for contacting catalyst in (iii) with gas streams, do not limit particularly System so that any conceivable gas hourly space velocity may be selected in principle to implement method of the invention, condition be it includes 100-30,000h-1In the range of.Thus, for example, contact of the catalyst in (iii) with gas streams can in 500-20, 000h-1, preferably 1,000-15,000h-1, more preferable 2,000-10,000h-1, more preferable 3,000-8,000h-1, more preferable 4, 000-6,000h-1, more preferable 4,500-5,500h-1Gas hourly space velocity (GHSV) under carry out.However, it is particularly preferred to catalysis Contact of the agent in (iii) with gas streams is in 4,800-5,200h-1Gas hourly space velocity (GHSV) under carry out.
, it is preferred according to the present invention that the zeolitic material has MOR framework structure in (i).
According to the present invention, in principle to the YO of the zeolitic material with MOR framework structure2:X2O3There is no limit for molar ratio, So that any conceivable YO may be selected2:X2O3Molar ratio implements method of the invention.Thus, for example, having MOR bone The zeolitic material of frame structure can show 5-100, preferably 6-70, more preferable 8-50, more preferable 10-40, more preferable 12-30, more It is preferred that the YO within the scope of 14-25, more preferable 16-202:X2O3Molar ratio.However, it is particularly preferred to have MOR framework structure Zeolitic material show the YO within the scope of 17-182:X2O3Molar ratio.
The quadrivalent element Y of zeolitic material used in the method for the present invention with MOR framework structure, without special Limitation, so that any conceivable quadrivalent element may be selected in principle to implement method of the invention.Thus, for example, Y can Selected from Si, Sn, Ti, Zr, Ge and its mixture of two or more.However, it is preferred according to the present invention that Y is Si.About The triad X of zeolitic material used in the method for the present invention with MOR framework structure, is not particularly limited, to make Obtaining may be selected any conceivable triad in principle to implement method of the invention.Thus, for example, X can be selected from Al, B, In, Ga and its mixture of two or more.However, it is preferred according to the present invention that X is Al and/or B, preferably Al.
, it is preferred according to the present invention that there is the H-shaped formula of zeolitic material of MOR framework structure and include proton as bone The outer ion of frame, wherein 0.1 weight % or less, preferably 0.05 weight % or less, more preferable 0.001 weight % or less, more It is preferred that 0.0005 weight % or the outer ion of less skeleton are metal cation, calculate based on the element and based on institute in zeolitic material The 100 weight %YO contained2.It is particularly preferred that there is the H-shaped formula of zeolitic material of MOR framework structure and include that proton is made For ion outside skeleton, wherein 0.0001 weight % or the outer ion of less skeleton are metal cation, calculate based on the element and base The 100 weight %YO contained in zeolitic material2。
Within the meaning of the present invention, " the outer ion of skeleton " refers to included in the micropore of zeolitic material and compensates zeolite bone The ion and/or ionic compound of the charge of frame, wherein preferred meaning according to the present invention, " the outer ion of skeleton ", which refers to, to be included in In the micropore of zeolitic material and compensate zeolite skeleton charge cation and/or cationic compound.
, it is preferred according to the present invention that the zeolitic material with MOR framework structure is made comprising one or more metal ions Ms It is more preferably selected from for ion outside skeleton wherein one or more metal ions Ms are selected from alkaline-earth metal and/or transition metal The 4th race of the periodic table of elements and 6-11 race, are preferably selected from the metal of the 4th race and 8-11 race, wherein it is more preferably described a kind of or Various metals ion M be selected from Mg, Ti, Cu, Co, Cr, Ni, Fe, Mo, Mn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, Sn, Zn, Ca, Mg and its mixture of two or more are more preferably selected from Cu, Sn, Zn, Ca, Mg and its mixture of two or more. It is particularly preferred that the zeolitic material with MOR framework structure includes Cu and/or Zn, preferably Cu is as the outer ion of skeleton.
About the content as the M of ion outside skeleton in the zeolitic material with MOR framework structure, do not limit particularly System, so that any M as ion outside skeleton that amount can be envisaged may be selected in principle to implement method of the invention.Cause This, for example, the zeolitic material may include 0.5-15 weight %, preferably 1-10 weight %, more preferable 1.3-8 weight % is more excellent 1.5-7 weight %, more preferable 1.8-6 weight %, more preferable 2-5.5 weight %, more preferable 2.3-5 weight % are selected, more preferably 2.5-4.5 weight %, more preferable 2.8-4 weight %, the M as ion outside skeleton of more preferable 3-3.5 weight %, based on the element It calculates and based on 100 weight %YO contained in zeolitic material2.However, it is particularly preferred to the boiling with MOR framework structure Stone material includes the M as ion outside skeleton of 3.1-3.4 weight %, is calculated based on the element and based on contained in zeolitic material 100 weight %YO2。
In addition, the M:X about the zeolitic material with MOR framework structure2O3Molar ratio is not particularly limited, to make Obtain may be selected any conceivable M:X in principle2O3Molar ratio implements method of the invention.Thus, for example, having MOR framework The M:X of the zeolitic material of structure2O3Molar ratio can be 0.01-2, preferably 0.05-1.5, more preferably 0.1-1, more preferably 0.2-0.8, more preferably 0.3-0.7, more preferably 0.35-0.65, more preferably 0.4-0.6.However, according to the present invention especially Preferably, the M:X of the zeolitic material with MOR framework structure2O3Molar ratio is 0.45-0.55.
, it is preferred according to the present invention that the zeolitic material is substantially free of Na, it is more excellent preferably substantially free from Na or K Choosing is substantially free of alkali metal, more preferably substantially free of alkali or alkaline earth metal.
Within the meaning of the present invention, the present invention is with regard to Na, K contained in zeolitic material skeleton, alkali or alkaline earth metal Measuring " substantially " that uses indicates 0.1 weight % or less, preferably 0.05 weight % or less, more preferable 0.001 weight % or Less, more preferable 0.0005 weight % or less, even more preferably 0.0001 weight % or less Na, K, alkali metal or alkaline earth Amount of metal is calculated based on the element and based on 100 weight %YO contained in the zeolitic material with MOR framework structure2。
, it is preferred according to the present invention that the average particle size along 002 axis of crystallite of the zeolitic material with MOR framework structure is 5 ± 1nm to 55 ± 8nm, is measured by powder x-ray diffraction.
About the zeolitic material with MOR framework structure measured by powder x-ray diffraction along the 5 of 002 axis of crystallite To 55 ± 8nm average particle size, those skilled in the art will be readily understood that can get by changing technological parameter in all ± 1nm Zeolitic material in the range.US 7,605,295B1 is disclosed in the 2nd column 8-13 row and 45-47 row comprising having The UZM aggregate material of the spheroidal aggravation of the crystallite of MOR framework type, the crystallite have about 60nm or smaller, preferably from about Average crystalline size of the 50nm or smaller along 002 axis of crystallite.
In addition, US 7,687,423B2 describes preparation with the MOR framework structure along 002 axis of crystallite in embodiment The method of zeolitic material, wherein being prepared in embodiment 1 with the average crystalline substance along 002 axis of crystallite for being respectively 47 and 50nm The UZM-14-A and UZM-14-B of body size.In addition, slightly changing its implementation in the embodiment 3 of US 7,687,423B2 Other UZM-14 samples are prepared under the parameter discussed in example 1, so that material obtained is with 40.6-50.4nm along micro- The average crystalline size of brilliant 002 axis.In addition, US 7,687,423B2 is emphasized, the prior art material obtained from Zeolist and Tosoh Expect the average crystalline size along 002 axis of crystallite for having greater than 55 ± 8nm.
In addition, the other embodiments and comparative example of this article provide acquisition on all for those skilled in the art State the further guide of the zeolitic material in range.
Preferably, the zeolitic material along 002 axis of crystallite granularity be 10 ± 1nm to 53 ± 8nm, more preferably 15 ± 2nm to 50 ± 5nm, more preferably 18 ± 2nm to 48 ± 5nm, more preferably 20 ± 2nm to 45 ± 5nm, more preferably 23 ± 2nm to 43 ± 4nm, more preferably 25 ± 3nm to 40 ± 4nm, more preferably 28 ± 3nm to 38 ± 4nm, more preferably 30 ± 3nm to 35 ± 4nm.It is particularly preferred that the zeolitic material along 002 axis of crystallite average particle size be 32 ± 3nm to 34 ± 3nm is measured by powder x-ray diffraction.
Or, it is preferred that by powder x-ray diffraction measure the zeolitic material along 002 axis of crystallite average grain Degree be 25 ± 3nm to 41 ± 4nm, preferably 26 ± 3nm to 40 ± 4nm, more preferably 27 ± 3nm to 39 ± 4nm, more preferably 28 ± 3nm to 38 ± 4nm, more preferably 29 ± 3nm are to 37 ± 4nm, more preferably 30 ± 3nm to 36 ± 4nm, more preferably 31 ± 3nm to 35 ± 4nm, more preferably 32 ± 3nm are to 34 ± 3nm.
Or, it is preferred that by powder x-ray diffraction measure the zeolitic material along 002 axis of crystallite average grain Degree be 38 ± 4nm to 54 ± 8nm, preferably 39 ± 4nm to 53 ± 8nm, more preferably 40 ± 4nm to 52 ± 5nm, more preferably 41 ± 4nm to 51 ± 5nm, more preferably 42 ± 4 to 50 ± 5nm, more preferably 43 ± 4nm to 49 ± 5nm, more preferably 44 ± 4nm to 48 ± 5nm, more preferably 45 ± 5nm are to 47 ± 5nm.
Or, it is preferred that by powder x-ray diffraction measure the zeolitic material along 002 axis of crystallite average grain Degree be 39 ± 4nm to 55 ± 8nm, preferably 40 ± 4nm to 54 ± 8nm, more preferably 41 ± 4nm to 53 ± 8nm, more preferably 42 ± 4nm to 52 ± 5nm, more preferably 43 ± 4nm are to 51 ± 5nm, more preferably 44 ± 4nm to 50 ± 5nm, more preferably 45 ± 5nm to 49 ± 5nm, more preferably 46 ± 5nm are to 48 ± 5nm.
Or, it is preferred that by powder x-ray diffraction measure the zeolitic material along 002 axis of crystallite average grain Degree be 45 ± 5nm to 55 ± 8nm, preferably 46 ± 5nm to 54 ± 8nm, more preferably 47 ± 5nm to 53 ± 8nm, more preferably 48 ± 5nm to 52 ± 8nm, more preferably 49 ± 5nm are to 51 ± 5nm.
About the zeolitic material by powder x-ray diffraction along the primary crystallites average particle size value of 002 axis of crystallite, it should be noted that , according to the present invention, described value is interpreted as comprising with lower deviation (size depending on the primary crystallites along 002 axis), institute State deviation is indicated with " ± " after given value:
> 100-200nm:20% (for example, for 150nm, ± 30nm),
> 50-100nm:15% (for example, for 100nm, ± 15nm),
> 5-50nm:10% (for example, for 50nm, ± 5nm),
2-5nm:20% (for example, for 5nm, ± 1nm).
About the zeolitic material with MOR framework structure measured by powder x-ray diffraction along the flat of 002 axis of crystallite Equal granularity measures it and is not particularly limited according to the present invention.However, it is preferred according to the present invention that there is MOR framework The zeolitic material of structure is according to method disclosed in US 7,687,423B2, especially along the average particle size value of 002 axis of crystallite The measurement as described in the 8th column 25-48 row of document.However, according to the present invention it may further be preferable that being penetrated by powder X-ray The zeolitic material with MOR framework structure of line diffraction along the average particle size value of 002 axis of crystallite is tested according to the application What method described in part determined, wherein described value is fitted diffraction peak width by using software TOPAS 4.2 and penetrates to be based on X Line diffraction data determine, wherein using TOPAS 4.2Users Manual (Bruker AXS GmbH, Rheinbr ü ckenstr.49,76187 Karlsruhe, Germany) described in basic parameter method carry out peak fitting during examine Consider instrumental broadening, so that instrumental broadening is separated with sample broadening, sample contribution uses single Lip river defined in following equation Hereby distribution function determines for human relations:
β=λ/(Lcos θ)
Wherein β is Lorentz full width at half maximum (FWHM) (FWHM), and λ is the X-ray wavelength of CuKa used radiation, and L is crystallite dimension, θ For the half of peak position angle of scattering.According to the preferred method, the crystallite dimension of 002 reflection is at from 21 ° to 24.2 ° (2 θ) It is determined in local data's refine around 002 reflection, wherein there is the unimodal of different crystallite dimensions to simulate peripheral reflection, The middle step-length using 0.02 ° (2 θ) ° (2 θ) from 2 ° to 70 with Bragg-Brentano geometry collects data.
, it is preferred according to the present invention that the zeolitic material with MOR framework structure measured by powder x-ray diffraction The average particle size of primary crystallites be 5 ± 1nm to 100 ± 15nm, preferably the average particle size of primary crystallites be 10 ± 1nm to 90 ± 14nm, more preferably 20 ± 2nm are to 85 ± 13nm, more preferably 30 ± 3nm to 80 ± 12nm, more preferably 35 ± 4nm to 75 ± 11nm, more preferably 40 ± 4nm are to 70 ± 11nm, and more preferably 45 ± 5nm to 65 ± 10nm, more preferably 50 ± 5nm are extremely 65±10nm.It is particularly preferred that the average particle size of the primary crystallites of the zeolitic material measured by powder x-ray diffraction is 55 ± 8nm to 65 ± 10nm.The average particle size value of primary crystallites about the zeolitic material measured by powder x-ray diffraction, is answered , it is noted that according to the present invention, described value is interpreted as comprising with lower deviation (size depending on primary crystallites), the deviation It is indicated with " ± " after given value:
> 100-200nm:20% (for example, for 150nm, ± 30nm)
> 50-100nm:15% (for example, for 100nm, ± 15nm)
> 5-50nm:10% (for example, for 50nm, ± 5nm)
2-5nm:20% (for example, for 5nm, ± 1nm)
Primary crystallites about the zeolitic material with MOR framework structure measured by powder x-ray diffraction are averaged Granularity measures it and is not particularly limited according to the present invention.However, it is preferred according to the present invention that passing through X-ray powder The average particle size of the primary crystallites of the zeolitic material with MOR framework structure of diffraction is determined according to Scherrer equation 's.However, according to the present invention it may further be preferable that the zeolite with MOR framework structure measured by powder x-ray diffraction The average particle size value of the primary crystallites of material is what the method according to the application experimental section determined, and wherein described value passes through Diffraction peak width is fitted to determine based on X ray diffracting data using software TOPAS 4.2, wherein using TOPAS 4.2Users Manual (Bruker AXS GmbH,Rheinbr ü ckenstr.49,76187Karlsruhe, moral State) described in basic parameter method carry out considering instrumental broadening during peak fitting so that instrumental broadening and sample broaden Separation, sample contribution are determined using single Lorentz distribution function defined in following equation:
β=λ/(Lcos θ)
Wherein β is Lorentz full width at half maximum (FWHM) (FWHM), and λ is the X-ray wavelength of CuKa used radiation, and L is primary crystallites Average particle size, θ be peak position angle of scattering half, wherein using 0.02 ° (2 θ) step-length from 2 ° to 70 ° (2 θ) with Bragg- Brentano geometry collects data.
, it is preferred according to the present invention that the catalyst provided in (i) includes the zeolitic material with MOR framework structure, In the zeolitic material with MOR framework structure preferably comprise it is one or more selected from modenite, UZM-14, [Ga-Si-O]- MOR, Ca-Q, LZ-211, not in lead zeolite (Maricopaite), Na-D, RMA-1 and its mixture of two or more Zeolite.According to the present invention it is particularly preferred that the zeolitic material is UZM-14 and/or modenite, preferably modenite.
Alternatively, or additionally, it is preferred according to the present invention that the catalyst provided in (i) includes to have GME skeleton The zeolitic material of structure, wherein with GME skeleton structure zeolitic material preferably comprise it is one or more selected from sodium chabazite, [Be-P-O]-GME, richness K sodium chabazite, the zero defect sodium chabazite of synthesis and its zeolite of the mixture of two or more. According to the present invention it is particularly preferred that the zeolitic material is sodium chabazite.
In addition, again as an alternative to the above or additionally, it is preferred according to the present invention that the catalyst provided in (i) Comprising the zeolitic material with FAU skeleton structure, wherein the zeolitic material with GME skeleton structure preferably comprises one or more The zeolite of group and its two or more mixture of the kind selected from its composition, wherein preferably, the zeolitic material is eight Face zeolite, ZSM-3, beryllium phosphate (Beryllo-phosphate) X, [Al-Ge-O]-FAU, CSZ-1, ECR-30, X zeolite (Linde X), zeolite Y (Linde Y), LZ-210, SAPO-37, ZSM-20, [Co-Al-P-O]-FAU, dehydrogenation Na-X, dehydrogenation US-Y, siliceous Na-Y, [Ga-Ge-O]-FAU, [Al-Ge-O]-FAU, Li-LSX, [Ga-Al-Si-O]-FAU, [Ga-Si-O]- FAU, trbasic zinc phosphate X (Zincophosphate X) and its mixture of two or more.It is particularly preferably described according to the present invention Zeolitic material is faujasite.
In addition, again as an alternative to the above or additionally, it is preferred according to the present invention that the catalysis provided in (i) Agent includes the zeolitic material with CHA skeleton structure, wherein the zeolitic material with CHA skeleton structure preferably comprises one kind or more Kind is selected from the zeolite such as the following group: (Ni (deta)2)-UT-6, chabasie, | Li-Na | [Al-Si-O]-CHA, DAF-5, Na- water chestnut boiling Stone, K- chabasie, LZ-218, Linde D, Linde R, MeAPSO-47, Phi, SAPO-34, SAPO-47, SSZ-13, SSZ- 62, UiO-21, three oblique christianites (Willhendersonite), ZK-14, ZYT-6 and its mixture of two or more, it is excellent Choosing selected from chabasie, | Li-Na | [Al-Si-O]-CHA, Na- chabasie, K- chabasie, SAPO-34, SAPO-47, SSZ-13, SSZ-62 and its mixture of two or more, be more preferably selected from chabasie, | Li-Na | [Al-Si-O]-CHA, Na- water chestnut boiling Stone, SAPO-34, SSZ-13 and its combination of two or more are more preferably selected from chabasie, SAPO-34, SSZ-13 and its two The combination of kind or more.According to the present invention it is particularly preferred that the zeolitic material is chabasie.
, it is preferred according to the present invention that after the gas streams provided in (ii) are contacted with the catalyst provided in (i) The gas streams of acquisition are shown greater than 5 in (iii), preferably 5-80, more preferable 5.5-50, more preferable 6-30, more preferably (+two Asia of ethane -1,2- diamines of 6.5-20, more preferable 7-15, more preferable 7.5-12, more preferable 8-11, more preferable 8.5-10.5 Ethyl triamine): (amino ethyl ethanolamine+piperazine) molar ratio (integral molar quantity of ethane -1,2- diamines and diethylenetriamines with The molar ratio of the integral molar quantity of amino ethyl ethanolamine and piperazine).According to the present invention it is particularly preferred that the offer in (ii) The gas streams that gas streams obtain in (iii) after contacting with the catalyst provided in (i) show (the ethane-of 9-10 1,2- diamines+diethylenetriamines): (amino ethyl ethanolamine+piperazine) molar ratio (ethane -1,2- diamines and diethylidene three The molar ratio of the integral molar quantity of the integral molar quantity and amino ethyl ethanolamine and piperazine of amine).
, it is preferred according to the present invention that the gas streams provided in the catalyst and (ii) that provide in (i) are in (iii) Any moment before contact does not implement the zeolitic material with MOR framework structure to remove X from its skeleton structure2O3's Processing, does not preferably implement to remove X from the zeolitic material2O3Processing.
Before the catalyst provided in (i) preferably wherein contacts in (iii) with the gas streams provided in (ii) Any moment the zeolitic material with MOR framework structure is not implemented from its skeleton structure to remove X2O3Processing sheet In invention meaning, this indicates to implement to remove from the skeleton structure of the zeolitic material to the zeolitic material at no time 5 moles of % or more, preferably 3 moles of % or more, more preferable 1 mole of % or more, more preferable 0.5 mole of % or more, more It is preferred that 0.1 mole of % or more, more preferable 0.05 mole of % or more, more preferable 0.01 mole of % or more, more preferable 0.005 Mole % or more, more preferable 0.001 mole of % or more, more preferable 0.0005 mole of % or more, more preferable 0.0001 rubs Your % or more2O3Processing (the contained 100 mole %X in the zeolitic material based on synthesis2O3)。
It is contacted in (iii) with the gas streams provided in (ii) according to the catalyst wherein preferably provided in (i) Preceding any moment does not implement the zeolitic material with MOR framework structure to remove X from the zeolitic material2O3Processing Meaning of the present invention, this indicate at no time to the zeolitic material implement from the zeolitic material remove 5 moles of % or More, preferably 3 moles of % or more, more preferable 1 mole of % or more, more preferable 0.5 mole of % or more, more preferable 0.1 rubs Your % or more, more preferable 0.05 mole of % or more, more preferable 0.01 mole of % or more, more preferable 0.005 mole of % or More, more preferable 0.001 mole of % or more, more preferable 0.0005 mole of % or more, more preferable 0.0001 mole of % or more More X2O3Processing (the contained 100 mole %X in the zeolitic material based on synthesis2O3)。
About in the method for the present invention it is preferable to use the zeolitic material with MOR framework structure preparation, without special Limitation, so that it is of the invention to implement that any conceivable zeolitic material with MOR framework structure may be selected in principle Method.However, it is preferred according to the present invention that the zeolitic material with MOR framework structure passes through method comprising the following steps Preparation:
(1) preparation includes at least one YO2Source, at least one X2O3Source, and include one or more as structure directing agent Organic formwork and/or mixture comprising crystal seed；
(2) make the crystalline mixture prepared in (i), to obtain the zeolitic material with MOR framework structure；
(3) it is optionally separated the zeolitic material obtained in (2)；
(4) zeolitic material optionally obtained in washing (2) or (3)；
(5) zeolitic material that is optionally dry and/or calcining acquisition in (2), (3) or (4)；
(6) ion exchange procedure optionally is implemented to the zeolitic material obtained in (2), (3), (4) or (5), wherein zeolite The outer ion of skeleton contained in material and H+Carry out ion exchange；
(7) ion exchange procedure optionally is implemented to the zeolitic material obtained in (2), (3), (4), (5) or (6), wherein The outer ion of skeleton contained in zeolitic material carries out ion exchange: alkaline earth with selected from one or more metal ions Ms such as the following group Metal and/or transition metal are preferably selected from the metal of the 4th race and 6-11 race of the periodic table of elements, are more preferably selected from the 4th race and 8-11 race, wherein it is highly preferred that one or more metal ions Ms be selected from Mg, Ti, Cu, Co, Cr, Ni, Fe, Mo, Mn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, Sn, Zn, Ca, Mg and its mixture of two or more, be more preferably selected from Cu, Sn, Zn, Ca, Mg and its mixture of two or more, wherein it is highly preferred that the outer ion of skeleton contained in zeolitic material and Cu and/ Or Zn, preferably Cu carry out ion exchange；
(8) zeolitic material that is optionally dry and/or calcining acquisition in (7).
Within the meaning of the present invention, term used herein " organic formwork " indicates that any conceivable template that is suitable for is situated between Lead the organic material of synthetic zeolite material, it is however preferred to have the zeolitic material of MOR type skeleton structure, even further preferably, it is suitable In synthesis UZM-14 and/or modenite.
, it is preferred according to the present invention that one or more organic formwork choosings contained in the mixture prepared in (1) The compound of the compound of self-contained tetra-allkylammonium and the Ji Phosphonium of Wan containing Si, is preferably selected from R containing tetraalkylammonium cation1R2R3R4N+Change Close object and the Ji phosphonium cation of Wan containing Si R1R2R3R4P+Compound, wherein R1、R2、R3And R4It indicates optionally to replace independently of one another And/or (the C of optionally branching1-C6) alkyl, preferably (C1-C5) alkyl, more preferable (C1-C4) alkyl, more preferable (C1-C3) alkyl, The methyl optionally replaced or ethyl are even more preferably indicated, wherein even more preferably R1、R2、R3And R4Indicate the second optionally replaced Base preferably indicates unsubstituted ethyl.
According to the present invention it may further be preferable that one or more R containing tetraalkylammonium cation1R2R3R4N+Chemical combination Object and/or the one or more Ji phosphonium cation of Wan containing Si R1R2R3R4P+Compound be salt, preferably one or more choosings The salt of the following group freely: halide, preferably chloride and/or bromide, more preferable chloride, hydroxide, sulfate, nitric acid Salt, phosphate, acetate and its mixture of two or more, are more preferably selected from chloride, hydroxide, sulfate and its The mixture of two or more, more preferable one or more R containing tetraalkylammonium cation1R2R3R4N+Compound and/ Or the one or more Ji phosphonium cation of Wan containing Si R1R2R3R4P+Compound be hydroxide and/or bromide, even more Preferably bromide.
, it is preferred according to the present invention that one or more organic formwork choosings contained in the mixture prepared in (1) From N, N, N, tetra- (C of N-1-C4) tetra- (C of alkylammonium and N, N, N, N-1-C4) Wan Ji phosphonium compounds are preferably selected from N, N, N, tetra- (C of N-1- C3) tetra- (C of alkylammonium and N, N, N, N-1-C3) Wan Ji phosphonium compounds are more preferably selected from N, N, N, tetra- (C of N-1-C2) alkylammonium and N, Tetra- (C of N, N, N-1-C2) Wan Ji phosphonium compounds are more preferably selected from N, N, N, tetra- (C of N-1-C2) tetra- (C of alkylammonium and N, N, N, N-1- C2) Wan Ji phosphonium compounds, are more preferably selected from N, N, N, N- tetraethyl ammonium compound, N, N, N, N- tetramethyl-ammonium compound, N, N, N, N- tetraethylphosphonium compound, N, N, N, N- tetramethyl phosphonium compound and its mixture of two or more, even more preferably One or more organic formworks include one or more N, N, N, N- tetraethyl ammonium or N, N, N, N- tetraethylphosphonium compound, It is preferred that one or more N, N, N, N- tetraethyl ammonium compound.
About the one or more organic formworks and YO in the mixture provided according to (1)2Organic formwork: YO2It rubs That ratio, is not particularly limited, so that any conceivable organic formwork: YO may be selected in principle2Molar ratio is implemented The preparation method of zeolitic material with MOR framework structure.Thus, for example, according to described one kind in the mixture of (1) offer Or a variety of organic formworks and YO2Organic formwork: YO2Molar ratio can be 0.005-0.14, preferably 0.01-0.3, more preferably 0.02-0.2, more preferably 0.025-0.14, more preferably 0.03-0.1, more preferably 0.035-0.08, more preferably 0.04- 0.06.However, according to the present invention it is particularly preferred that according to one or more organic moulds in the mixture of (1) offer Plate and YO2Organic formwork: YO2Molar ratio is 0.045-0.055.
According to the present invention also it is preferred that preparation and the mixture crystallized in (2) are substantially free of except can in (1) The organic formwork being optionally included in except the organic formwork being preferably used as in the micropore of the zeolitic material of crystal seed, it is highly preferred that (1) it is prepared in and the mixture crystallized in (2) is substantially free of an organic template.
It is prepared in (1) wherein and is substantially free of an organic the meaning of the present invention of template in (2) middle mixture crystallized Interior, this indicates the preparation in (1) and the mixture crystallized in (2) can be only comprising based on 100 weights contained in the mixture Measure %YO2For 0.1 weight % or the organic formwork of less amount, it is preferably based on 100 weight %YO contained in the mixture2For 0.05 weight % or less, more preferable 0.001 weight % or less, more preferable 0.0005 weight % or less, even more preferably The organic formwork of 0.0001 weight % or less amount.If the organic formwork of the amount be all present in (1) preparation and In the mixture crystallized in (2), then it is alternatively referred to as " impurity " or " trace " in the meaning of present invention.Moreover, it should be noted that Term " organic formwork " and " Organic structure directing agent " use synonymously in the present application.However, it is preferred according to the present invention that (1) mixture prepared in includes one or more organic formworks as structure directing agent.
, it is preferred according to the present invention that being prepared in (1) and in (2) middle mixture crystallized substantially free of zeolite material Material is preferably prepared in (1) and in (2) middle mixture crystallized substantially free of crystal seed.
It prepares and in (2) middle mixture crystallized in (1) substantially free of zeolitic material wherein, preferably substantially not In meaning of the present invention containing crystal seed, this indicates the preparation in (1) and the mixture crystallized in (2) can be only comprising being based on the mixing 100 weight %YO contained in object2For 0.1 weight % or less amount, it is preferably based on 100 weight % contained in the mixture YO2For 0.05 weight % or less, more preferable 0.001 weight % or less, more preferable 0.0005 weight % or less, even more Preferably 0.0001 weight % or the zeolitic material of less amount preferably can only include the crystal seed of above-mentioned amount.If zeolitic material The amount of (preferably crystal seed), which is all present in, to be prepared in (1) and in (2) in mixture of crystallization, then in meaning of the present invention It is interior to be alternatively referred to as " impurity " or " trace ".
, it is preferred according to the present invention that the zeolite with MOR framework structure being preferred in the method for the present invention in preparation In (6) of the method for material, to zeolitic material implement ion exchange program, described program the following steps are included:
(6.a) implements ion exchange procedure to the zeolitic material obtained in (2), (3), (4) or (5), wherein zeolitic material Contained in the outer ion of skeleton and NH4+Carry out ion exchange；
(6.b) calcines the zeolitic material through ion exchange obtained in (6.a), to obtain the zeolitic material of H-shaped formula.
It about the calcining in (5), (6.b), (8) and/or (12), is not particularly limited, so that may be selected any Conceivable temperature and/or time implement to have the preparation method of the zeolitic material of MOR framework structure.
Thus, for example, the calcining in (5), (6.b), (8) and/or (12) can be at 200-850 DEG C, preferably 250-800 DEG C, More preferably 300-750 DEG C, more preferable 350-700 DEG C, more preferable 400-650 DEG C, more preferable 450-620 DEG C, more preferable 500-600 DEG C, it is carried out at a temperature of more preferable 520-580 DEG C.However, according to the present invention it is particularly preferred that (5), (6.b), (8) and/or (12) calcining in 540-560 DEG C at a temperature of carry out.
In addition, for example, (5), (6.b), (8) and/or the zeolitic material in (12) calcining can be with intermittent mode, partly connect Discontinuous Conduction mode or continuous mode carry out.Calcining in (6.b) is by being heated to zeolitic material according to defined herein The temperature of any specific and implementation embodiment and at such a temperature holding 0.5-36 hours, preferably 1-32 hours, more preferably It is 2-28 hours, 4-24 hours more preferable, it is 6-20 hours more preferable, it is 8-18 hours more preferable, more preferable 10-14 hours and carry out 's.However, according to the present invention it is particularly preferred that the calcining of (5), (6.b), (8) and/or the zeolitic material in (12) is to pass through By zeolitic material heat 11.5-12.5 hour and progress.When with the implementation of semicontinuous or continuous mode, calcination time corresponds to Zeolitic material is with the residence time in semi-continuous mode or the given calcining furnace of continuous mode operation.
In the case where this method is with fairly large implementation, calcining is preferably carried out with semi-continuous mode or continuous mode, more It is preferred that carrying out in a continuous mode.Even further preferably, the zeolitic material in (5), (6.b), (8) and/or (12) is calcined with continuous Mode is carried out with 0.2-50.0kg zeolitic material/hour, preferably 0.5-2.0kg zeolitic material/hour rate.It is excellent to can be used for this The conceivable device of the continuous calcining of choosing includes such as belt calciner and/or rotary calciner, wherein it is preferable to use rotations Calcining furnace.
However, according to the present invention it is particularly preferred that if to obtaining with one or more metal ions Ms in (7) The zeolitic material that ion exchange occurs is heat-treated such as drying and/or is calcined, then the processing is not related to 540 DEG C or higher Temperature, be not preferably related to 520 DEG C or higher, more preferable 500 DEG C or higher, more preferable 450 DEG C or higher, more preferable 400 DEG C or It is higher, more preferable 350 DEG C or higher, more preferable 300 DEG C or higher, more preferable 250 DEG C or higher, more preferable 200 DEG C or higher Temperature.According to the present invention it is particularly preferred that is obtained in (7) occurs ion exchange with one or more metal ions Ms Zeolitic material do not suffer from 150 DEG C or higher temperature.Therefore, it according to the particularly preferred embodiment, is obtained in (7) With one or more metal ions Ms occur ion exchange zeolitic material do not suffer from according to any specific and preferred of the application The calcining of (8) defined in embodiment.
In addition, according to the present invention it is particularly preferred that calcining in (6.b) 540-560 DEG C at a temperature of carry out, the time It is 11.5-12.5 hours.
, it is preferred according to the present invention that ion exchange is carried out to zeolitic material in (7), to obtain 0.1-10 weight %, preferably 0.5-8 weight % are measured, more preferable 1-6 weight %, more preferable 1.2-5 weight %, more preferable 1.5-4 weight % is more excellent Select 1.8-3.5 weight %, more preferable 2-3 weight %, one or more metal ions Ms of more preferable 2.3-2.9 weight % Load capacity in zeolitic material is calculated with one or more element Ms and based on 100 weights contained in zeolitic material Measure %YO2.According to the present invention it is particularly preferred that in (7), ion exchange occurs for the zeolitic material with MOR framework structure, To obtain load capacity of the one or more metal ions Ms of 2.5-2.7 weight % in zeolitic material, with described one kind Or multiple element M is calculated and based on 100 weight %YO contained in zeolitic material2.About being used to prepare with MOR framework knot The element Y of the zeolitic material of structure, is not particularly limited, so that any conceivable quadrivalent element may be selected in principle Implement the preparation method with the zeolitic material of MOR framework structure.Thus, for example, Y can be selected from Si, Sn, Ti, Zr, Ge and its two The combination of kind or more.However, according to the present invention it is particularly preferred that Y is Si.
, it is preferred according to the present invention that described in used in method of the preparation with the zeolitic material of MOR framework structure extremely A kind of few YO2Source includes one or more compounds selected from silica, silicate and its mixture, is preferably selected from pyrolysismethod Silica, silica hydrosol, reactive amorphous solid silica, silica gel, silicic acid, waterglass, sodium metasilicate water It closes object, sesquisilicate, dislicata, colloidal silicon dioxide, esters of silicon acis, tetraalkoxysilane and its two or more is mixed Object is closed, pyrogenic silica, silica hydrosol, silica gel, silicic acid, waterglass, colloidal silicon dioxide, silicon are more preferably selected from Acid esters, tetraalkoxysilane and its mixture of two or more are more preferably selected from pyrogenic silica, silica water Colloidal sol, silica gel, colloidal silicon dioxide and its mixture of two or more, be more preferably selected from pyrogenic silica, silica gel, Colloidal silicon dioxide and its mixture of two or more, the more preferable at least one YO2Source is selected from fumed silica Silicon, colloidal silicon dioxide and its mixture.According to the present invention it is particularly preferred that using pyrogenic silica as YO2Source.
About the element X for being used to prepare the zeolitic material with MOR framework structure, it is not particularly limited, so that Any conceivable triad may be selected in principle to implement to have the preparation method of the zeolitic material of MOR framework structure.Cause This, for example, X can be selected from Al, B, In, Ga and its combination of two or more.However, it is preferred according to the present invention that X is Al。
, it is preferred according to the present invention that described in used in method of the preparation with the zeolitic material of MOR framework structure extremely A kind of few X2O3Source includes one or more aluminium salts, and the aluminate of preferred as alkali, wherein alkali metal is preferably selected from Li, Na, K, Rb And Cs, wherein more preferable alkali metal is Na and/or K, wherein even more preferably alkali metal is Na.
YO about the mixture prepared in (1)2:X2O3Molar ratio is not particularly limited, so that in principle may be used Select any conceivable YO2:X2O3Molar ratio implements to have the preparation method of the zeolitic material of MOR framework structure.Therefore, For example, the YO of the mixture prepared in (1)2:X2O3Molar ratio can be 2-50, preferably 4-40, more preferably 6-35, more preferably For 10-30, more preferably 13-25, more preferably 15-23, more preferably 17-22.However, particularly preferred according to the present invention It is the YO of the mixture prepared in (1)2:X2O3Molar ratio is 19-21.
Crystalline substance about the method for being used to prepare the zeolitic material with MOR framework structure being preferred in the method for the present invention Kind, it is not particularly limited, so that can appoint in principle for the preparation method selection of the zeolitic material with MOR framework structure What conceivable crystal seed.Thus, for example, crystal seed may include zeolitic material, preferably one or more zeolites are more preferably a kind of or more Kind has the zeolite of BEA skeleton structure, wherein more preferable crystal seed includes zeolite beta.However, according to the present invention it is particularly preferred that Use zeolite beta as the crystal seed for the mixture being used to prepare in (1).
This is equally applicable to the crystal seed amount with the preparation method of the zeolitic material of MOR framework structure, and condition is can to prepare Zeolitic material with MOR framework structure.Thus, for example, the crystal seed amount in the mixture prepared in (1) can be 0.1-15 weight Measure %, preferably 0.5-10 weight %, more preferably 0.8-8 weight %, more preferably 1-5 weight %, more preferably 1.3-3 weight % is measured, based on 100 weight %YO contained in the mixture2.However, according to the present invention it is particularly preferred that preparation in (1) Crystal seed amount in mixture is 1.5-2.5 weight %.
, it is preferred according to the present invention that the mixture prepared in (1) further includes the solvent containing one or more solvents System, wherein the dicyandiamide solution preferably comprises one or more solvents selected from polar aprotic solvent and its mixture, preferably Selected from n-butanol, isopropanol, propyl alcohol, ethyl alcohol, methanol, water and its mixture, it is more preferably selected from ethyl alcohol, methanol, water and its mixing Object, wherein more preferably the dicyandiamide solution includes water.According to the present invention it is particularly preferred that using water, preferably deionized water is made For the dicyandiamide solution in (1) in the mixture of preparation.
According to the present invention it may further be preferable that when the preparation in (1) and the mixture crystallized in (2) include it is a kind of or When a variety of organic formworks, and when the mixture prepared in (1) comprises water as dicyandiamide solution, the mixture of preparation in (1) H2O:YO2Molar ratio is 5-70, preferably 10-65, more preferably 15-60, more preferably 20-55, more preferably 25-50, more Preferably 30-47, more preferably 35-45, more preferably 37-43.According to the present invention it is particularly preferred that when the preparation in (1) And when the mixture of crystallization includes one or more organic formworks in (2), and when the mixture prepared in (1) includes water work When for dicyandiamide solution, the H of the mixture prepared in (1)2O:YO2Molar ratio is 39-41.
According to the present invention it may further be preferable that the mixture of crystallization includes crystal seed when the preparation in (1) and in (2) When, and when the mixture prepared in (1) comprises water as dicyandiamide solution, the H of the mixture prepared in (1)2O:YO2Mole Than for 5-45, preferably 10-40, more preferably 12-35, more preferably 15-30, more preferably 17-27, more preferably 19-25. According to the present invention it is particularly preferred that when the preparation in (1) and when (2) middle mixture crystallized includes crystal seed, and when (1) When the mixture of middle preparation comprises water as dicyandiamide solution, the H of the mixture prepared in (1)2O:YO2Molar ratio is 21-23.
, it is preferred according to the present invention that the mixture prepared in (1) further includes one or more alkali metal (AM), it is excellent One or more alkali metal selected from Li, Na, K, Cs and its mixture are selected, the mixture prepared in more preferable (1) further wraps Containing Na and/or K, more preferable Na is as alkali metal AM.
About when in the preparation in (1) and (1) when (2) middle mixture crystallized includes one or more organic formworks Alkali metal and YO in the mixture of preparation2AM:YO2Molar ratio is not particularly limited, so that can be present invention side In method it is preferable to use the preparation method of the zeolitic material with MOR framework structure select any conceivable AM:YO2Mole Than.Thus, for example, when the preparation in (1) and when (2) middle mixture crystallized includes one or more organic formworks, in (1) Alkali metal and YO in the mixture of preparation2AM:YO2Molar ratio can be 0.01-1.5, preferably 0.05-1, more preferably 0.08-0.5, more preferably 0.1-0.35, more preferably 0.12-0.3, more preferably 0.15-0.25.It is particularly preferred, however, that It is, when being prepared in (1) and the mixture crystallized in (2) includes one or more organic formworks, the mixing of preparation in (1) Alkali metal and YO in object2AM:YO2Molar ratio is 0.18-0.22.
The alkali in mixture prepared in (1) about the preparation in (1) and when the mixture crystallized in (2) includes crystal seed Metal and YO2AM:YO2Molar ratio is not particularly limited so that can in the method for the present invention it is preferable to use have The preparation method of the zeolitic material of MOR framework structure selects any conceivable AM:YO2Molar ratio.Thus, for example, when in (1) Middle preparation and alkali metal and YO when (2) middle mixture crystallized includes crystal seed, in (1) middle mixture prepared2AM:YO2 Molar ratio can be 0.3-2, preferably 0.5-1.5, more preferably 0.8-1.2, more preferably 1-1, more preferably 1.2-0.8, more Preferably 1.3-0.5.However, according to the present invention it is particularly preferred that when the preparation in (1) and the mixture crystallized in (2) Alkali metal and YO when comprising crystal seed, in (1) in the mixture of preparation2AM:YO2Molar ratio is 1.35-1.4.
It is furthermore preferred according to the present invention that the YO of the mixture prepared in (1)2:X2O3: AM molar ratio is 1:(0.02- 0.5): (0.1-2), preferably 1:(0.025-0.25): (0.2-1.5), more preferably 1:(0.029-0.17): (0.3-1.4), More preferably 1:(0.033-0.1): (0.4-1.2), more preferably 1:(0.04-0.08): (0.5-1), more preferably 1: (0.043-0.7): (0.55-0.9), more preferably 1:(0.045-0.06): (0.6-0.8).It is particularly preferred that system in (1) The YO of standby mixture2:X2O3: AM molar ratio is 1:(0.045-0.05): (0.65-0.75).
It about the crystallization in (2), is not particularly limited, so that in principle can be the boiling with MOR framework structure The preparation method of stone material selects any conceivable crystallization condition.
Thus, for example, the crystallization in (2) may include heating the mixture prepared in (1), it is preferably heated to 75-210 DEG C, More preferably 90-200 DEG C, more preferable 110-190 DEG C, more preferable 130-175 DEG C, more preferable 140-165 DEG C of temperature.According to this hair It is bright it is particularly preferred that the crystallization in (2) includes the temperature that the mixture prepared in (1) is heated to 145-155 DEG C.
In addition, preferably being carried out under the conditions of solvent heat for example, the crystallization in (2) can carry out at autogenous pressures.According to this Invention is it is particularly preferred that the crystallization in (2) carries out under hydrothermal conditions.
, it is preferred according to the present invention that working as the preparation in (1) and having in (2) middle mixture crystallized comprising one or more When machine template, the crystallization in (2) includes that the mixture that will be prepared in (1) heats 50-115 hours, 60-95 hours more preferable, more It is preferred that 65-85 hours, 70-80 hours more preferable, more preferable 70-78 hours of the time.According to the present invention it is particularly preferred that working as The preparation and when the mixture crystallized in (2) includes one or more organic formworks in (1), the crystallization in (2) includes by (1) The mixture of middle preparation heats 75-77 hours time.
, it is preferred according to the present invention that when the preparation in (1) and when (2) middle mixture crystallized includes crystal seed, in (2) Crystallization include that the mixture that will be prepared in (1) heats 60-140 hours, 70-120 hours more preferable, more preferable 75-100 is small When, more preferable 80-90 hours of the time.According to the present invention it is particularly preferred that when the preparation in (1) and the crystallization in (2) When mixture includes crystal seed, the crystallization in (2) includes the time that the mixture that will be prepared in (1) heats 82-86 hours.
, it is preferred according to the present invention that the zeolitic material with MOR framework structure crystallized in (2) is modenite.
, it is preferred according to the present invention that being prepared in (1) and in (2) middle mixture crystallized substantially free of phosphorus.
Within the meaning of the present invention, for the preparation in (1) and the phosphorus amount contained in (2) middle mixture crystallized, " substantially " that the present invention uses indicates 0.1 weight % or less, preferably 0.05 weight % or less, more preferable 0.001 weight Measure % or less, more preferable 0.0005 weight % or less, even more preferably 0.0001 weight % or the phosphorus of less amount, with member Element calculates and based on 100 weight %YO in mixture2.Within the meaning of the present invention, preparation and the knot in (2) in (1) Brilliant mixture includes element phosphor and phosphorus-containing compound substantially free of the definition of phosphorus.
, it is preferred according to the present invention that the skeleton of the zeolitic material obtained in (2) preferably obtains in (2) substantially free of phosphorus The zeolitic material obtained is substantially free of phosphorus.
Within the meaning of the present invention, for phosphorus amount contained in the skeleton of the zeolitic material obtained in (2), the present invention makes " substantially " 0.1 weight % or less, preferably 0.05 weight % or less, more preferable 0.001 weight % or less are indicated, More preferable 0.0005 weight % or less, even more preferably 0.0001 weight % or the phosphorus of less amount, calculate based on the element and Based on 100 weight %YO in zeolitic material2.In addition, within the meaning of the present invention, institute in the zeolitic material just obtained in (2) For the phosphorus amount contained, " substantially " that the present invention uses indicates 0.1 weight % or less, preferably 0.05 weight % or less, more It is preferred that 0.001 weight % or less, more preferable 0.0005 weight % or less, even more preferably 0.0001 weight % or less The phosphorus of amount is calculated based on the element and based on 100 weight %YO in zeolitic material2.Within the meaning of the present invention, it is obtained in (2) Zeolitic material skeleton in substantially free of the phosphorus be free of in preparation and the mixture crystallized in (2) preferably in (1) Definition includes element phosphor and phosphorus-containing compound.
According to the present invention, for can be used in the methods of the invention catalyst in provide with MOR framework structure The form of zeolitic material is not particularly limited.Therefore, the zeolitic material can use as former state, or can be together with other components It uses.Therefore, with the method for the invention it is preferred to which zeolitic material is included in used in the method for the present invention in the form of moulded work In catalyst.Therefore it is preferred according to the present invention, that boiling of the preparation according to any particular preferred embodiment described herein The preferred method of stone material further comprises:
9) zeolitic material obtained in (2), (3), (4), (5), (6), (7) or (8) and one or more adhesives is mixed It closes；
(10) mixture obtained in (9) is mediated；
(11) kneaded mixture obtained in (10) is molded, to obtain one or more moulded works；With
(12) one or more moulded works that are dry and/or calcining acquisition in (11).
For the one or more adhesives that can be mixed with the zeolitic material obtained in (7) or (8), without special Limitation so that any suitable adhesive can be used in principle.Thus, for example, one or more adhesives can Selected from inorganic bond, wherein, it is preferred according to the present invention that one or more adhesives include one or more metals Oxide and/or quasi-metal oxide source or one or more graphitic sources, wherein one or more metal oxides and/or Quasi-metal oxide source be preferably selected from silica, aluminium oxide, titanium dioxide, zirconium oxide, lanthana, magnesia and its two kinds or More kinds of mixtures and/or mixed oxide are more preferably selected from silica, aluminium oxide, titanium dioxide, zirconium oxide, oxidation Magnesium, silica-alumina mixed oxide, silica-titania mixed oxide, silica-zirconium oxide mixing Oxide, silica-zirconia lanthanum mixed oxide, silica-zirconium oxide-lanthana mixed oxide, aluminium oxide-dioxy Change titanium mixed oxide, alumina-silica Zr mixed oxide, alumina-lanthania mixed oxide, aluminium oxide-zirconium oxide- Lanthana mixed oxide, titania-zirconia mixed oxide and its mixture of two or more and/or mixing oxygen Compound is more preferably selected from silica, aluminium oxide, silica-alumina mixed oxide and its two or more is mixed Close object.However, according to the present invention it is particularly preferred that one or more adhesives include one or more silica, Aluminium oxide, zirconium oxide and/or graphitic source, wherein more preferable adhesive is by one or more silica, aluminium oxide, zirconium oxide And/or graphitic source composition, wherein more preferably one or more adhesives include one or more silica, aluminium oxide And/or zirconia source, wherein even more preferably adhesive is by one or more silica, aluminium oxide and/or zirconia source group At being preferably made of silica, aluminium oxide and/or zirconia source.
, it is preferred according to the present invention that by ethane -1,2- glycol contained in the gas streams obtained in (iii) and/or 2- ethylaminoethanol separates from the gas streams and is recycled to (ii).
Of the invention is further characterized by following and particularly preferred embodiment, including is indicated by corresponding adduction relationship Combination and embodiment:
1. a kind of convert ethane -1,2- diamines and/or formula H for ethane -1,2- glycol2N-[CH2CH2NH]n- CH2CH2NH2L-PEI method, wherein n >=1, which comprises
(i) it provides comprising containing YO2And X2O3Zeolitic material catalyst, wherein Y be quadrivalent element, X is triad, Wherein the zeolitic material is selected from the zeolitic material with MOR, FAU, CHA and/or GME skeleton structure, including its two kinds or more A variety of combinations；
(ii) gas streams comprising the pure and mild ammonia of ethane -1,2- two are provided；
(iii) contact the catalyst provided in (i) with the gas streams provided in (ii), thus by ethane -1,2- bis-
Alcohol is converted into ethane -1,2- diamines and/or L-PEI,
Wherein n is preferably 1-8, more preferably 1-5, more preferably 1-4, more preferably 1-3, more preferably 1-2, wherein more It is preferred that n=1.
2. the method for embodiment 1, wherein the gas streams packet for providing in (ii) and being contacted in (iii) with catalyst Containing in an amount of from 0.1-10 volume %, preferably 0.5-5 volume %, more preferably 1-4.5 volume %, more preferably 1.5-4 body Product %, more preferably 2-3.7 volume %, more preferably 2.5-3.5 volume %, more preferably 2.7-3.3 volume %, more preferably Ethane -1,2- the glycol of 2.9-3.1 volume %.
3. the method for embodiment 1 or 2, wherein the gas material for providing in (ii) and being contacted in (iii) with catalyst Stream is comprising in an amount of from 5-90 volume %, preferably 10-80 volume %.More preferably 20-70 volume %, more preferably 25-60 body Product %, more preferably 30-50 volume %, more preferably 35-45 volume %, more preferably 37-43 volume %, more preferably 39- The ammonia of 41 volume %.
4. the method for any one of embodiment 1-3, wherein providing in (ii) and being contacted in (iii) with catalyst Ammonia in gas streams: ethane -1,2- glycol molar ratio is 1-45, preferably 2-35, more preferably 4-30, more preferably 6- 25, more preferably 8-20, more preferably 10-16, more preferably 12-14.
5. the method for any one of embodiment 1-4, wherein providing in (ii) and being contacted in (iii) with catalyst Gas streams are further included in an amount of from 0.1-70 volume %, preferably 0.5-50 volume %, more preferably 1-40 volume %, more Preferably 5-35 volume %, more preferably 10-30 volume %, more preferably 15-25 volume %, more preferably 17-23 volume %, The more preferably hydrogen of 19-21 volume %.
6. the method for any one of embodiment 1-4, wherein providing in (ii) and being contacted in (iii) with catalyst Gas streams include 1 volume % or less hydrogen, preferably 0.5 volume % or less, more preferable 0.1 volume % or less, more It is preferred that 0.05 volume % or less, more preferable 0.001 volume % or less, more preferable 0.0005 volume % or less, more preferably 0.0001 volume % or less hydrogen.
7. the method for any one of embodiment 1-6, wherein providing in (ii) and being contacted in (iii) with catalyst Gas streams are further included in an amount of from 5-90 volume %, preferably 10-80 volume %, more preferably 20-70 volume %, more excellent It is selected as 25-60 volume %, more preferably 30-50 volume %, more preferably 35-45 volume %, more preferably 37-43 volume %, The more preferably inert gas of 39-41 volume %.
8. the method for embodiment 7, wherein inert gas includes one or more gases selected from such as the following group: rare gas Body, N2And its mixture of two or more, it is preferably selected from He, Ne, Ar, N2And its mixture of two or more, wherein More preferable inert gas includes Ar and/or N2, preferably N2, wherein it is highly preferred that inert gas is Ar and/or N2, preferably N2。
9. the method for any one of embodiment 1-8, wherein providing in (ii) and being contacted in (iii) with catalyst Gas streams contain in an amount of from 5 volume % or less, preferably 3 volume % or less, more preferably 1 volume % or less, more Preferably 0.5 volume % or less, more preferably 0.1 volume % or less, more preferably 0.05 volume % or less, more preferably For 0.01 volume % or less, more preferable 0.005 volume % or less, more preferable 0.001 volume % or less, more preferably 0.0005 volume % or less, more preferably 0.0001 volume % or less H2O。
10. the method for any one of embodiment 1-9, wherein the gas streams provided in (ii) are heated to 120-600 DEG C temperature, then contacted in (iii) with catalyst at such a temperature, the temperature is preferably 150-550 DEG C, more preferably 180-500 DEG C, more preferably 200-450 DEG C, more preferably 230-400 DEG C, more preferably 250-370 DEG C, more preferably 270- 350 DEG C, more preferably 280-320 DEG C, more preferably 290-310 DEG C.
11. the method for any one of embodiment 1-10, wherein contact of the catalyst in (iii) with gas streams exists 0.05-20MPa, preferably 0.1-10MPa, more preferable 0.3-5MPa, more preferable 0.5-3MPa, more preferable 0.6-2MPa, more preferably 0.7-1.5MPa, more preferable 0.8-1.3MPa are carried out under the pressure of more preferable 0.9-1.1MPa.
12. the method for any one of embodiment 1-11, wherein contact of the catalyst in (iii) with gas streams exists 100-30,000h-1, preferably 500-20,000h-1, more preferable 1,000-15,000h-1, more preferable 2,000-10,000h-1, more excellent Select 3,000-8,000h-1, more preferable 4,000-6,000h-1, more preferable 4,500-5,500h-1, more preferable 4,800-5,200h-1 Gas hourly space velocity (GHSV) under carry out.
13. the method for any one of embodiment 1-12, wherein the zeolitic material has MOR framework knot in (i) Structure.
14. the method for any one of embodiment 1-13, wherein the zeolitic material shows 5-100, preferably 6-70, more It is preferred that 8-50, more preferable 10-40, more preferable 12-30, more preferable 14-25, more preferable 16-20, the YO of more preferable 17-182:X2O3 Molar ratio.
15. the method for any one of embodiment 1-14, wherein Y be selected from Si, Sn, Ti, Zr, Ge and its two or more Mixture, Y is preferably Si.
16. the method for any one of embodiment 1-15, wherein X is selected from Al, B, In, Ga and its two or more is mixed Object is closed, X is preferably Al and/or B, more preferably Al.
17. the method for any one of embodiment 1-16, the wherein H-shaped formula of zeolitic material and include proton as skeleton Outer ion, wherein 0.1 weight % or less, preferably 0.05 weight % or less, more preferable 0.001 weight % or less is more excellent 0.0005 weight % or less is selected, more preferable 0.0001 weight % or the outer ion of less skeleton are metal cation, with element It calculates and based on 100 weight %YO contained in zeolitic material2。
18. the method for any one of embodiment 1-17, wherein zeolitic material includes one or more metal ions M conducts The outer ion of skeleton is more preferably selected from member wherein one or more metal ions Ms are selected from alkaline-earth metal and/or transition metal The metal of plain periodic table the 4th race and 6-11 race, is preferably selected from the 4th race and 8-11 race, wherein more preferably described a kind of or more Metal ion species M is selected from Mg, Ti, Cu, Co, Cr, Ni, Fe, Mo, Mn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, Sn, Zn, Ca, Mg And its mixture of two or more, it is more preferably selected from Cu, Sn, Zn, Ca, Mg and its mixture of two or more, In more preferably zeolitic material include Cu and/or Zn, preferably Cu as skeleton outside ion.
19. the method for embodiment 18, wherein zeolitic material includes 0.5-15 weight %, preferably 1-10 weight %, more excellent 1.3-8 weight %, more preferable 1.5-7 weight %, more preferable 1.8-6 weight %, more preferable 2-5.5 weight % are selected, more preferably 2.3-5 weight %, more preferable 2.5-4.5 weight %, more preferable 2.8-4 weight %, more preferable 3-3.5 weight %, more preferably The M of 3.1-3.4 weight % is calculated and as the outer ion of skeleton based on 100 weight % contained in zeolitic material based on the element YO2。
20. the method for embodiment 18 or 19, the wherein M:X of zeolitic material2O3Molar ratio is 0.01-2, preferably 0.05- 1.5, more preferably 0.1-1, more preferably 0.2-0.8, more preferably 0.3-0.7, more preferably 0.35-0.65, more preferably 0.4-0.6, more preferably 0.45-0.55.
21. the method for any one of embodiment 1-20, wherein zeolitic material is substantially free of Na, preferably substantially free from Na or K, more preferably substantially free of alkali metal, more preferably substantially free of alkali or alkaline earth metal.
22. the method for any one of embodiment 1-21, wherein the zeolitic material with MOR framework structure is along crystallite 002 The average particle size of axis is 5 ± 1nm to 55 ± 8nm, is measured by powder x-ray diffraction.
23. the method for embodiment 22, wherein the zeolitic material measured by powder x-ray diffraction is along 002 axis of crystallite Granularity be 10 ± 1nm to 53 ± 8nm, preferably 15 ± 2nm to 50 ± 5nm, more preferably 18 ± 2nm to 48 ± 5nm, more preferably For 20 ± 2nm to 45 ± 5nm, more preferably 23 ± 2nm to 43 ± 4nm, more preferably 25nm ± 3nm to 40 ± 4nm, more preferably For 28 ± 3nm to 38 ± 4nm, more preferably 30 ± 3nm to 35 ± 4nm, more preferably 32 ± 3nm to 34 ± 3nm.
24. the method for embodiment 22, wherein the zeolitic material measured by powder x-ray diffraction is along 002 axis of crystallite Average particle size be 25 ± 3nm to 41 ± 4nm, preferably 26 ± 3nm to 40 ± 4nm, more preferably 27 ± 3nm to 39 ± 4nm, more Preferably 28 ± 3nm to 38 ± 4nm, more preferably 29 ± 3nm are more excellent to 37 ± 4nm, more preferably 30 ± 3nm to 36 ± 4nm It is selected as 31 ± 3nm to 35 ± 4nm, more preferably 32 ± 3nm to 34 ± 3nm.
25. the method for embodiment 22, wherein the zeolitic material measured by powder x-ray diffraction is along 002 axis of crystallite Average particle size be 38 ± 4nm to 54 ± 8nm, preferably 39 ± 4nm to 53 ± 8nm, more preferably 40 ± 4nm to 52 ± 5nm, more Preferably 41 ± 4nm to 51 ± 5nm, more preferably 42 ± 4nm are more excellent to 50 ± 5nm, more preferably 43 ± 4nm to 49 ± 5nm It is selected as 44 ± 4nm to 48 ± 5nm, more preferably 45 ± 5nm to 47 ± 5nm.
26. the method for embodiment 22, wherein the zeolitic material measured by powder x-ray diffraction is along 002 axis of crystallite Average particle size be 39 ± 4nm to 55 ± 8nm, preferably 40 ± 4nm to 54 ± 8nm, more preferably 41 ± 4nm to 53 ± 8nm, more Preferably 42 ± 4nm to 52 ± 5nm, more preferably 43 ± 4nm are more excellent to 51 ± 5nm, more preferably 44 ± 4nm to 50 ± 5nm It is selected as 45 ± 5nm to 49 ± 5nm, more preferably 46 ± 5nm to 48 ± 5nm.
27. the method for embodiment 22, wherein the zeolitic material measured by powder x-ray diffraction is along 002 axis of crystallite Average particle size be 45 ± 5nm to 55 ± 8nm, preferably 46 ± 5nm to 54 ± 8nm, more preferably 47 ± 5nm to 53 ± 8nm, more Preferably 48 ± 5nm to 52 ± 8nm, more preferably 49 ± 5nm are to 51 ± 5nm.
28. the method for any one of embodiment 1-27, wherein there is MOR framework by what powder x-ray diffraction measured The average particle size of the primary crystallites of the zeolitic material of structure is 5 ± 1nm to 100 ± 15nm, wherein it is preferred that primary crystallites are averaged Partial size be 10 ± 1nm to 90 ± 14nm, more preferably 20 ± 2nm to 85 ± 13nm, more preferably 30 ± 3nm to 80 ± 12nm, More preferably 35 ± 4nm to 75 ± 11nm, more preferably 40 ± 4nm to 70 ± 11nm, more preferably 45 ± 5nm to 65 ± 10nm, more preferably 50 ± 5nm are to 65 ± 10nm, more preferably 55 ± 8nm to 65 ± 10nm.
29. the method for any one of embodiment 1-28, wherein the catalyst provided in (i) includes to have MOR framework knot The zeolitic material of structure, wherein the zeolitic material with MOR framework structure preferably comprises the zeolite of one or more choosings such as the following group: silk Geolyte, UZM-14, [Ga-Si-O]-MOR, Ca-Q, LZ-211, not in lead zeolite, Na-D, RMA-1 and its two or more Mixture, wherein preferred zeolite material is UZM-14 and/or modenite, preferably modenite.
30. the method for any one of embodiment 1-29, wherein the catalyst provided in (i) includes to have GME skeleton knot The zeolitic material of structure, wherein the zeolitic material with GME skeleton structure preferably comprises one or more zeolites selected from the group below: sodium Chabasie, [Be-P-O]-GME, richness K sodium chabazite, synthesis zero defect sodium chabazite and its mixture of two or more, Wherein preferred zeolite material is sodium chabazite.
31. the method for any one of embodiment 1-30, wherein the catalyst provided in (i) includes to have FAU skeleton knot The zeolitic material of structure, wherein the zeolitic material with FAU skeleton structure preferably comprises one or more zeolites selected from such as the following group: Faujasite, ZSM-3, beryllium phosphate X, [Al-Ge-O]-FAU, CSZ-1, ECR-30, X zeolite (Linde X), zeolite Y (Linde Y), LZ-210, SAPO-37, ZSM-20, [Co-Al-P-O]-FAU, dehydrogenation Na-X, dehydrogenation US-Y, siliceous Na-Y, [Ga-Ge- O]-FAU, [Al-Ge-O]-FAU, Li-LSX, [Ga-Al-Si-O]-FAU, [Ga-Si-O]-FAU, trbasic zinc phosphate X and its two kinds or More kinds of mixtures, wherein it is preferred that the zeolitic material is faujasite.
32. the method for any one of embodiment 1-31, wherein the catalyst provided in (i) includes to have CHA skeleton knot The zeolitic material of structure, wherein the zeolitic material with CHA skeleton structure preferably comprises one or more zeolites selected from the group below: (Ni(deta)2)-UT-6, chabasie, | Li-Na | [Al-Si-O]-CHA, DAF-5, Na- chabasie, K- chabasie, LZ-218, Linde D, Linde R, MeAPSO-47, Phi, SAPO-34, SAPO-47, SSZ-13, SSZ-62, UiO-21, three oblique potassium boilings Stone, ZK-14, ZYT-6 and its mixture of two or more, be preferably selected from chabasie, | Li-Na | [Al-Si-O]-CHA, Na- chabasie, K- chabasie, SAPO-34, SAPO-47, SSZ-13, SSZ-62 and its mixture of two or more, it is more excellent Choosing selected from chabasie, | Li-Na | [Al-Si-O]-CHA, Na- chabasie, SAPO-34, SSZ-13 and its two or more Combination, is more preferably selected from chabasie, SAPO-34, SSZ-13 and its combination of two or more, wherein the more preferably zeolite Material is chabasie.
33. the method for any one of embodiment 1-32, wherein provided in the gas streams provided in (ii) and (i) The gas streams of acquisition are shown greater than 5 in (iii) after catalyst contact, preferably 5-80, more preferably 5.5-50, more Preferably 6-30, more preferably 6.5-20, more preferably 7-15, more preferably 7.5-12, more preferably 8-11, more preferably (ethane -1, the 2- diamines+diethylenetriamines) of 8.5-10.5, more preferably 9-10: (amino ethyl ethanolamine+piperazine) mole Than (integral molar quantity of ethane -1,2- diamines and diethylenetriamines rubs with the integral molar quantity of amino ethyl ethanolamine and piperazine That ratio).
34. the method for any one of embodiment 1-33, wherein the gas provided in the catalyst and (ii) that are provided in (i) At any moment of the body stream in (iii) before contact, the zeolitic material with MOR framework structure is not implemented from its skeleton X is removed in structure2O3Processing, preferably do not implement to remove X from the zeolitic material2O3Processing.
35. the method for any one of embodiment 1-34, wherein the zeolitic material with MOR framework structure by include with It is prepared by the method for lower step:
(1) preparation includes at least one YO2Source, at least one X2O3Source, and include one or more as structure directing agent Organic formwork and/or mixture comprising crystal seed；
(2) make the crystalline mixture prepared in (i), to obtain the zeolitic material with MOR framework structure；
(3) it is optionally separated the zeolitic material obtained in (2)；
(4) zeolitic material optionally obtained in washing (2) or (3)；
(5) zeolitic material that is optionally dry and/or calcining acquisition in (2), (3) or (4)；
(6) ion exchange procedure optionally is implemented to the zeolitic material obtained in (2), (3), (4) or (5), wherein zeolite The outer ion of skeleton contained in material and H+Carry out ion exchange；
(7) ion exchange procedure optionally is implemented to the zeolitic material obtained in (2), (3), (4), (5) or (6), wherein The outer ion of skeleton contained in zeolitic material carries out ion exchange: alkaline earth with selected from one or more metal ions Ms such as the following group Metal and/or transition metal are preferably selected from the metal of the 4th race and 6-11 race of the periodic table of elements, are more preferably selected from the 4th race and 8-11 race, wherein it is highly preferred that one or more metal ions Ms be selected from Mg, Ti, Cu, Co, Cr, Ni, Fe, Mo, Mn, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, Sn, Zn, Ca, Mg and its mixture of two or more, be more preferably selected from Cu, Sn, Zn, Ca, Mg and its mixture of two or more, wherein it is highly preferred that the outer ion of skeleton contained in zeolitic material and Cu and/ Or Zn, preferably Cu carry out ion exchange；
(8) zeolitic material that is optionally dry and/or calcining acquisition in (7).
36. the method for embodiment 35, wherein one or more organic moulds contained in the mixture prepared in (1) Plate is selected from the compound of the compound containing tetra-allkylammonium and the Ji Phosphonium of Wan containing Si, is preferably selected from R containing tetraalkylammonium cation1R2R3R4N+ Compound and the Ji phosphonium cation of Wan containing Si R1R2R3R4P+Compound, wherein R1、R2、R3And R4It indicates independently of one another optional (the C of branching replace and/or optional1-C6) alkyl, preferably (C1-C5) alkyl, more preferable (C1-C4) alkyl, more preferable (C1-C3) Alkyl even more preferably indicates the methyl optionally replaced or ethyl, wherein even more preferably R1、R2、R3And R4It indicates optionally to replace Ethyl, preferably indicate unsubstituted ethyl.
37. the method for embodiment 36, wherein one or more R containing tetraalkylammonium cation1R2R3R4N+Chemical combination Object and/or the one or more Ji phosphonium cation of Wan containing Si R1R2R3R4P+Compound be salt, preferably one or more choosings The salt of the following group freely: halide, preferably chloride and/or bromide, more preferable chloride, hydroxide, sulfate, nitric acid Salt, phosphate, acetate and its mixture of two or more, are more preferably selected from chloride, hydroxide, sulfate and its The mixture of two or more, wherein more preferably one or more R containing tetraalkylammonium cation1R2R3R4N+Compound And/or the one or more Ji phosphonium cation of Wan containing Si R1R2R3R4P+Compound be hydroxide and/or bromide, even More preferably bromide.
38. the method for any one of embodiment 35-37, wherein described one kind contained in the mixture prepared in (1) Or a variety of organic formworks are selected from N, N, N, tetra- (C of N-1-C4) tetra- (C of alkylammonium and N, N, N, N-1-C4) Wan Ji phosphonium compounds, preferably Selected from N, N, N, tetra- (C of N-1-C3) tetra- (C of alkylammonium and N, N, N, N-1-C3) Wan Ji phosphonium compounds, are more preferably selected from N, N, N, N- Four (C1-C2) tetra- (C of alkylammonium and N, N, N, N-1-C2) Wan Ji phosphonium compounds are more preferably selected from N, N, N, tetra- (C of N-1-C2) alkyl Ammonium and N, N, N, tetra- (C of N-1-C2) Wan Ji phosphonium compounds are more preferably selected from N, N, N, N- tetraethyl ammonium compound, N, N, N, N- tetra- Methyl ammonium compounds, N, N, N, N- tetraethylphosphonium compound, N, N, N, N- tetramethyl phosphonium compound and its two or more Mixture, even more preferably described one or more organic formworks include one or more N, N, N, N- tetraethyl ammonium or N, N, N, N- tetraethylphosphonium compound, preferably one or more N, N, N, N- tetraethyl ammonium compound.
39. the method for any one of embodiment 35-38, wherein described a kind of in the mixture provided according to (1) or A variety of organic formworks and YO2Organic formwork: YO2Molar ratio is 0.005-0.14, preferably 0.01-0.3, more preferably 0.02- 0.2, more preferably 0.025-0.14, more preferably 0.03-0.1, more preferably 0.035-0.08, more preferably 0.04-0.06, More preferably 0.045-0.055.
40. the method for embodiment 35, wherein preparation and the mixture crystallized in (2) are substantially free of removing in (1) The organic formwork that can be optionally included in except the organic formwork being preferably used as in the micropore of the zeolitic material of crystal seed, wherein more preferably Ground, prepares in (1) and the mixture crystallized in (2) is substantially free of an organic template.
41. the method for any one of embodiment 35-40, wherein preparation and the mixture base crystallized in (2) in (1) Zeolitic material is free of in sheet, wherein preferably, preparing in (1) and in (2) middle mixture crystallized substantially free of crystal seed.
42. the method for any one of embodiment 35-41, wherein carrying out ion exchange procedure to zeolitic material in (6) The step of the following steps are included:
(6.a) implements ion exchange procedure to the zeolitic material obtained in (2), (3), (4) or (5), wherein zeolitic material Contained in the outer ion of skeleton and NH4+Carry out ion exchange；
(6.b) calcines the zeolitic material through ion exchange obtained in (6.a), to obtain the zeolitic material of H-shaped formula.
43. the method for embodiment 42, wherein the calcining in (5), (6.b), (8) and/or (12) is at 200-850 DEG C, it is excellent Select 250-800 DEG C, more preferable 300-750 DEG C, more preferable 350-700 DEG C, more preferable 400-650 DEG C, more preferable 450-620 DEG C, It is carried out at a temperature of more preferably 500-600 DEG C, more preferable 520-580 DEG C, more preferable 540-560 DEG C.
44. the method for embodiment 42 or 43, wherein the calcining of (5), (6.b), (8) and/or the zeolitic material in (12) Be by by zeolitic material calcine 0.5-36 hours, it is preferably 1-32 hours, 2-28 hours more preferable, it is 4-24 hours more preferable, more It is 8-18 hours more preferable it is preferred that 6-20 hours, it is 10-14 hours more preferable, more preferable 11.5-12.5 hours of the time and carry out 's.
45. the method for any one of embodiment 35-44, wherein ion exchange is carried out to zeolitic material in (7), thus Obtain 0.1-10 weight %, preferably 0.5-8 weight %, more preferable 1-6 weight %, more preferable 1.2-5 weight %, more preferable 1.5- 4 weight %, more preferable 1.8-3.5 weight %, more preferable 2-3 weight %, more preferable 2.3-2.9 weight %, more preferable 2.5-2.7 Load capacity of the one or more metal ions Ms of weight % in zeolitic material is calculated with one or more element Ms And based on 100 weight %YO contained in zeolitic material2。
46. the method for any one of embodiment 35-45, wherein Y be selected from Si, Sn, Ti, Zr, Ge and its two or more The combination of kind, Y is preferably Si.
47. the method for any one of embodiment 35-46, wherein at least one YO2Source includes one or more choosings From the compound of silica, silicate and its mixture,
Be preferably selected from pyrogenic silica, silica hydrosol, reactive amorphous solid silica, silica gel, Silicic acid, waterglass, sodium metasilicate hydrate, sesquisilicate, dislicata, colloidal silicon dioxide, esters of silicon acis, tetraalkoxy silicon Alkane and its mixture of two or more,
It is more preferably selected from pyrogenic silica, silica hydrosol, silica gel, silicic acid, waterglass, colloidal silica Silicon, esters of silicon acis, tetraalkoxysilane and its mixture of two or more,
It is more preferably selected from pyrogenic silica, silica hydrosol, silica gel, colloidal silicon dioxide and its two kinds or more A variety of mixtures,
It is more preferably selected from pyrogenic silica, silica gel, colloidal silicon dioxide and its mixture of two or more,
The wherein more preferably at least one YO2Source is selected from pyrogenic silica, colloidal silicon dioxide and its mixture,
Wherein more preferably use pyrogenic silica as YO2Source.
48. the method for any one of embodiment 35-47, wherein X be selected from Al, B, In, Ga and its two or more Combination, X is preferably Al.
49. the method for any one of embodiment 35-48, wherein at least one X2O3Source includes one or more aluminium Salt, preferred as alkali aluminate, wherein the alkali metal is preferably selected from Li, Na, K, Rb and Cs, wherein the more preferably alkali metal For Na and/or K, wherein the even more preferably described alkali metal is Na.
50. the method for any one of embodiment 35-49, wherein the YO of the mixture prepared in (1)2:X2O3Molar ratio is 2-50, preferably 4-40, more preferably 6-35, more preferably 10-30, more preferably 13-25, more preferably 15-23, more preferably For 17-22, more preferably 19-21.
51. the method for any one of embodiment 35-50, wherein crystal seed includes zeolitic material, preferably one or more boilings Stone, more preferable one or more zeolites with BEA skeleton structure, wherein more preferable crystal seed includes zeolite beta, wherein more preferably making Use zeolite beta as the crystal seed for being used to prepare mixture in (1).
52. the method for any one of embodiment 35-51, wherein the crystal seed amount in the mixture prepared in (1) is 0.1- 15 weight %, preferably 0.5-10 weight %, more preferably 0.8-8 weight %, more preferably 1-5 weight %, more preferably 1.3-3 weight %, more preferably 1.5-2.5 weight %, based on 100 weight %YO contained in the mixture2。
53. the method for any one of embodiment 35-52, wherein the mixture prepared in (1) is further included containing one kind Or the dicyandiamide solution of multi-solvents, wherein dicyandiamide solution preferably comprises one or more selected from polar aprotic solvent and its mixture Solvent,
It is preferably selected from n-butanol, isopropanol, propyl alcohol, ethyl alcohol, methanol, water and its mixture,
It is more preferably selected from ethyl alcohol, methanol, water and its mixture,
Wherein it is highly preferred that dicyandiamide solution includes water, wherein more preferably using water, it is preferable to use deionized water is as solvent System.
54. the method for embodiment 53, wherein preparation and the mixture crystallized in (2) include a kind of or more in (1) Kind organic formwork, and the mixture wherein prepared in (1) comprises water as dicyandiamide solution, wherein the mixture prepared in (1) H2O:YO2Molar ratio be preferably 5-70, preferably 10-65, more preferably 15-60, more preferably 20-55, more preferably 25-50, more preferably 30-47, more preferably 35-45, more preferably 37-43, more preferably 39-41.
55. the method for embodiment 53, wherein preparation and the mixture crystallized in (2) include crystal seed in (1), and The mixture wherein prepared in (1) comprises water as dicyandiamide solution, wherein the H of the mixture prepared in (1)2O:YO2Molar ratio is excellent It is selected as 5-45, preferably 10-40, more preferably 12-35, more preferably 15-30, more preferably 17-27, more preferably 19-25, More preferably 21-23.
56. the method for any one of embodiment 35-55, wherein the mixture prepared in (1) further include it is a kind of or A variety of alkali metal (AM), preferably one or more alkali metal selected from Li, Na, K, Cs and its mixture, wherein more preferably in (1) The mixture of preparation further includes Na and/or K, and more preferable Na is as alkali metal M.
57. the method for embodiment 56, wherein preparation and the mixture crystallized in (2) include a kind of or more in (1) Kind organic formwork, and alkali metal and YO in the mixture wherein prepared in (1)2AM:YO2Molar ratio is 0.01-1.5, excellent It is selected as 0.05-1, more preferably 0.08-0.5, more preferably 0.1-0.35, more preferably 0.12-0.3, more preferably 0.15- 0.25, more preferably 0.18-0.22.
58. the method for embodiment 56, wherein preparation and the mixture crystallized in (2) include crystal seed in (1), and The alkali metal and YO in mixture wherein prepared in (1)2AM:YO2Molar ratio is 0.3-2, preferably 0.5-1.5, more preferably For 0.8-1.2, more preferably 1-1, more preferably 1.2-0.8, more preferably 1.3-0.5, more preferably 1.35-1.4.
59. the method for any one of embodiment 56-58, wherein the YO of the mixture prepared in (1)2:X2O3: AM moles Than for 1:(0.02-0.5): (0.1-2), preferably 1:(0.025-0.25): (0.2-1.5), more preferably 1:(0.029- 0.17): (0.3-1.4), more preferably 1:(0.033-0.1): (0.4-1.2), more preferably 1:(0.04-0.08): (0.5- 1), more preferably 1:(0.043-0.7): (0.55-0.9), more preferably 1:(0.045-0.06): (0.6-0.8), more preferably 1:(0.045-0.05):(0.65-0.75)。
60. the method for any one of embodiment 35-59, wherein the crystallization in (2) includes the mixing prepared in heating (1) Object, is preferably heated to 75-210 DEG C, and more preferable 90-200 DEG C, more preferable 110-190 DEG C, more preferable 130-175 DEG C, more preferably 140-165 DEG C, more preferable 145-155 DEG C of temperature.
61. the method for any one of embodiment 35-60 preferably exists wherein the crystallization in (2) carries out at autogenous pressures It carries out under the conditions of solvent heat, more preferably carries out under hydrothermal conditions.
62. the method for any one of embodiment 35-61, wherein preparation and the mixture packet crystallized in (2) in (1) Containing one or more organic formworks, and wherein, the crystallization in (2) includes mixture heating 50-115 that will prepare in (1) small When, 60-95 hours more preferable, 65-85 hours more preferable, 70-80 hours more preferable, 70-78 hours more preferable, more preferable 75- 77 hours time.
63. the method for any one of embodiment 35-62, wherein preparation and the mixture packet crystallized in (2) in (1) Containing crystal seed, and wherein, the crystallization in (2) includes that the mixture that will be prepared in (1) heats 60-140 hours, more preferable 70-120 Hour, 75-100 hours more preferable, 80-90 hours more preferable, more preferable 82-86 hours of the time.
64. the method for any one of embodiment 35-63, wherein the one kind with MOR framework structure crystallized in (2) Or a variety of zeolites are modenite.
65. the method for any one of embodiment 35-64, wherein preparation and the mixture base crystallized in (2) in (1) It is not phosphorous in sheet.
66. the method for any one of embodiment 35-65, wherein the skeleton of the zeolitic material obtained in (2) is substantially not It is phosphorous, wherein it is preferred that the zeolitic material obtained in (2) is substantially free of phosphorus.
67. the method for any one of embodiment 35-66, wherein the zeolitic material obtained in (7) does not suffer from 540 DEG C or more Height, more preferable 520 DEG C or higher, more preferable 500 DEG C or higher, more preferable 450 DEG C or higher, more preferable 400 DEG C or higher, more It is preferred that 350 DEG C or higher, more preferable 300 DEG C or higher, more preferable 250 DEG C or higher, more preferable 200 DEG C, more preferable 150 DEG C or Higher temperature.
68. the method for any one of embodiment 35-67, the method further includes:
9) zeolitic material obtained in (2), (3), (4), (5), (6), (7) or (8) and one or more adhesives is mixed It closes；
(10) mixture obtained in (9) is mediated；
(11) kneaded mixture obtained in (10) is molded, to obtain one or more moulded works；With
(12) one or more moulded works that are dry and/or calcining acquisition in (11).
69. the method for embodiment 68, wherein one or more adhesives are selected from inorganic bond, wherein described one Kind or a variety of adhesives preferably comprise one or more metal oxides and/or quasi-metal oxide source or one or more graphite Source, wherein one or more metal oxides and/or quasi-metal oxide source are preferably selected from silica, aluminium oxide, two Titanium oxide, zirconium oxide, lanthana, magnesia and its mixture of two or more and/or mixed oxide, are more preferably selected from Silica, aluminium oxide, titanium dioxide, zirconium oxide, magnesia, silica-alumina mixed oxide, silica-two Aoxidize titanium mixed oxide, silica-zirconium oxide mixed oxide, silica-zirconia lanthanum mixed oxide, titanium dioxide Silicon-zirconium oxide-lanthana mixed oxide, aluminium oxide-titanium dioxide mixed oxide, alumina-silica Zr mixed oxide, Alumina-lanthania mixed oxide, aluminium oxide-zirconium oxide-lanthana mixed oxide, titania-zirconia mixing oxygen Compound and its mixture of two or more and/or mixed oxide, are more preferably selected from silica, aluminium oxide, titanium dioxide Silicon-oxidation aluminium-mixed oxide and its mixture of two or more, wherein more preferably one or more adhesive packets Containing one or more silica, aluminium oxide, zirconium oxide and/or graphitic source, preferably described one or more adhesives include one Kind or a variety of silica, aluminium oxide and/or zirconia source, wherein more preferable described adhesive is by one or more titanium dioxides Silicon, aluminium oxide and/or zirconia source composition, are preferably made of silica, aluminium oxide and/or zirconia source.
70. the method for any one of embodiment 1-69, wherein by second contained in the gas streams obtained in (iii) Alkane -1,2- glycol and/or 2- ethylaminoethanol separate from the gas streams and are recycled to (ii).
Detailed description of the invention
Fig. 1 shows the x-ray diffractogram of powder of the Na- modenite obtained in embodiment 4, wherein for the mesh compared , it include the linear map of the Na-Type Mordenit from crystallography data library.X ray diffracting spectrum shown in figure be using Cu K α -1 actinometry.In corresponding diffraction pattern, 2 θ (°) of the angle of diffraction is shown along abscissa, is depicted by force along ordinate Degree.
Embodiment
Crystallite dimension is measured using X-ray diffraction method
The crystallite dimension of sample is fitted diffraction peak width by using 4.2 software of TOPAS, uses X-ray diffraction measure. Use according to TOPAS 4.2Users Manual (Bruker AXS GmbH,Rheinbr ü ckenstr.49, 76187Karlsruhe, Germany) described in basic parameter method carry out peak fitting during consider instrumental broadening.This leads to instrument Broadening is separated with sample broadening.Sample contribution is determined using single Lorentz distribution function defined in following equation:
β=λ/(Lcos θ)
Wherein β is Lorentz full width at half maximum (FWHM) (FWHM), and λ is the X-ray wavelength of CuKa used radiation, and L is crystallite dimension, θ For the half of peak position angle of scattering.
The crystallite dimension of 002 reflection in sample with MOR framework type is in the 002 anti-of from 21 ° to 24.2 ° (2 θ) Penetrate determination in local data's refine of surrounding.Unimodal with different crystallite dimensions simulates peripheral reflection.
Using the step-length of 0.02 ° (2 θ), data are collected in the Bragg-Brentano geometry of 2 ° to 70 ° (2 θ).
Relative intensity ratio (RIR) method
In the examples below, the relative quantity of the GME and CHA type skeleton structure in each sample is quantitative by X-ray diffraction Using Chung, F.H., in Journal of Applied Crystallography, volume 7, the 6th phase, the 519-525 pages, The measurement of relative intensity ratio (RIR) method described in December, 1974, this is a kind of Unmarked word method without calibration.For this purpose, The diffraction number for analysis is collected on D8Advance Series II diffractometer (Bruker AXS GmbH, Karlsruhe) According to.It is configured using LYNXEYE detector (window is set as 3 ° of openings) with Bragg-Brentano geometry.Using being set as 0.3 ° of fixation divergent slit and 5 ° (2q) collect data to the angular range of 70 ° (2q).Step size settings are 0.02 ° (2q), Selection sweep time is to obtain at least 50.000 peak strengths counted.Then, by with software package DIFFRAC.EVA V2 (Bruker AXS GmbH, Karlsruhe, referring to DIFFRAC.SUITE User Manual, DIFFRAC.EVA, 2011, Page 111) X ray diffracting data is analyzed to determine the relative quantity of each GME and CHA skeleton phase in sample.Use Acta Cryst. (2002), PDF database described in B58,333-337 identifies the crystalline phase in sample.Use respective entries in database I/IcorValue, these values describe the most strong diffraction maximum of respective compound relative to the corundum principal reflection in 50% mixture Relative intensity.
The synthesis of embodiment 1:H- modenite
606,49g sodium metasilicate (waterglass) is placed in 5L plastic beaker, and is added thereto under the stirring of 200rpm rate Enter 61.09g sodium aluminate and is dissolved in the solution formed in 748,05g distilled water to gel is formed, then under the rate further Stirring 1 hour.Then under the stirring rate of 150rpm, 374.25g colloidal silicon dioxide aqueous solution (40 is added into mixture Weight %；Ludox AS-40), and gained mixture is stirred 3 hours under the rate.Finally, the H-shaped formula of 31.2g is added Zeolite beta (CP 814-C, Zeolyst), and mixture is futher stirred 1 hour at 150rpm, thus obtaining pH is 12 Gel, by its aged overnight.
Then, make to show that mole group becomes 1.38Na2O:0.15Al2O3:SiO2:21.7H2O and include 2 weight % crystal seeds (based on 100 weight %SiO in mixture2Calculate) synthesized gel rubber in closed at 170 DEG C in 250rpm stirring rate Stirring under crystallize 84 hours.Then, it filters out and is washed with deionized using products therefrom as solid, until the electricity of washing water Conductance reaches the value lower than 150 μ S.Then, solid is 12 hours dry at 90 DEG C in air.Then, by solid in air In with 3.5 DEG C/min of the rate of heat addition be heated to 90 DEG C, then kept for 2 hours at said temperatures.Then, by solid with 1.5 DEG C/min the rate of heat addition be heated to 120 DEG C, then at said temperatures keep 2 hours.Then, by solid with 4.5 DEG C/minute The rate of heat addition of clock is heated to 550 DEG C and is kept for 12 hours at said temperatures.Yield is 286g.
According to elemental analysis, the every 100g substance of products therefrom measures content with following: 0.1g carbon, 6.0g aluminium, 5.2g sodium With 34g silicon.
Measuring BET surface area is 354m2/g.The crystallinity for measuring product is 84%.
Can be seen that gained zeolitic material from the X-ray diffractogram of products therefrom shows MOR framework structure as monocrystalline Phase.
The 100g ammonium nitrate in 900g distilled water is dissolved in as aqueous solution (10 weight %NH4NO3) it is placed in 2L stirring dress In setting, 100g zeolitic material is added, and gained mixture is stirred 2 hours at 80 DEG C.Then zeolitic material is filtered out, then will The 10 new aqueous solutions of weight % of the 100g ammonium nitrate comprising being dissolved in 900g distilled water are placed in agitating device, are added thereto Washed zeolitic material, and gained mixture is stirred 2 hours at 80 DEG C again.Then, filter out zeolitic material and with steam Distilled water washing, until washing water is free of nitrate.Then, washed material is 5 hours dry at 120 DEG C, then 500 It is calcined 5 hours at DEG C, the rate of heat addition is 2 DEG C/min.Then entire program is repeated, to obtain the zeolite material of the H-shaped formula of 85g Material.
According to elemental analysis, the every 100g substance of gained sample measures content with following: < 0.1g carbon, 6.1g aluminium, 0.01g Sodium and 35g silicon.
Measuring BET surface area is 403m2/g。
The synthesis of embodiment 2:H- modenite
In 5L plastic beaker, 120g pyrogenic silica (CAB-O-SIL M5, Sigma-Aldrich) is suspended in In 900g deionized water.Into the suspension be added 52.04g tetraethylammonium bromide (TEABr, Aldrich) in 161.7g go from Mixture in sub- water.Gained mixture is stirred 1 hour under the stirring rate of 200rpm.Then, 36.5g hydroxide is added Mixture of the sodium piece (NaOH, Sigma-Aldrich) in 161.7g deionized water.Then, by gained mixture in 300rpm Stirring rate under stir 1.5 hours.Then, 188.6g deionized water is added, 15.66g sodium aluminate (NaAlO is then added2, Sigma-Aldrich) the mixture in 188.6g deionized water.Then, by gained mixture 200rpm stirring rate Lower stirring 1 hour.The pH value for measuring the mixture is 12.5.Gel is formed, by its aged overnight.
Then, make to show that mole group becomes 0.28Na2O:0.048Al2O3:SiO2:44.5H2The conjunction of O:0.13 TEABr It is crystallized 84 hours under the stirring of 250rpm stirring rate at 170 DEG C in closed container at gel.Then, by products therefrom It filters out and is washed with deionized as solid, until the conductivity of washing water reaches the value lower than 150 μ S.Then, by solid It is 12 hours dry at 90 DEG C in air.Then, solid is heated to 90 in air with 3.5 DEG C/min of the rate of heat addition DEG C, then kept for 2 hours at said temperatures.Then, solid is heated to 120 DEG C with 1.5 DEG C/min of the rate of heat addition, so It is kept for 2 hours at said temperatures afterwards.Then, solid with 4.5 DEG C/min of the rate of heat addition is heated to 550 DEG C and described At a temperature of kept for 12 hours.Yield is 66g.
According to elemental analysis, the every 100g substance of products therefrom measures content with following: 0.1g carbon, 5.0g aluminium, 3.2g sodium With 37g silicon.
Measuring BET surface area is 382m2/g.The crystallinity for measuring product is 86%.
Can be seen that gained zeolitic material from the X-ray diffractogram of products therefrom shows MOR framework structure as monocrystalline Phase, wherein being determined as 58nm by the average crystalline size along 002 axis of crystallite that X ray diffracting data calculates.
The 50g ammonium nitrate in 450g distilled water is dissolved in as aqueous solution (10 weight %NH4NO3) it is placed in 2L stirring dress In setting, 50g zeolitic material is added, gained mixture is stirred 2 hours at 80 DEG C.Then zeolitic material is filtered out, it then will packet The 10 new aqueous solutions of weight % containing the 50g ammonium nitrate being dissolved in 450g distilled water are placed in agitating device, and filter is added thereto Zeolitic material out again stirs gained mixture 2 hours at 80 DEG C.Then, it filters out zeolitic material and is washed with distillation It washs, until washing water is free of nitrate.Then, washed material is 5 hours dry at 120 DEG C, then forged at 500 DEG C It burns 5 hours, the rate of heat addition is 2 DEG C/min.Then entire program is repeated, to obtain the zeolitic material of the H-shaped formula of 43.7g.
According to elemental analysis, the every 100g substance of gained sample measures content with following: < 0.1g carbon, 4.9g aluminium, 0.06g Sodium and 38g silicon.
Measuring BET surface area is 432m2/g。
The synthesis of embodiment 3:H- modenite
In 5L plastic beaker, 120g pyrogenic silica (CAB-O-SIL M5, Sigma-Aldrich) is suspended in In 900g deionized water.Into the suspension be added 52.04g tetraethylammonium bromide (TEABr, Aldrich) in 161.7g go from Mixture in sub- water.Gained mixture is stirred 1 hour under the stirring rate of 200rpm.Then, 36.5g hydroxide is added Mixture of the sodium piece (NaOH, Sigma-Aldrich) in 161.7g deionized water.Then, by gained mixture in 300rpm Stirring rate under stir 1.5 hours.188.6g deionized water is then added, 15.66g sodium aluminate (NaAlO is then added2, Sigma-Aldrich) the mixture in 188.6g deionized water.Then, by gained mixture 200rpm stirring rate Lower stirring 1 hour.The pH value for measuring mixture is 12.2.Gel is formed, by its aged overnight.
Then, make to show that mole group becomes 0.28Na2O:0.048Al2O3:SiO2:44.5H2The synthesis of O:0.13TEABr Gel crystallizes 72 hours under the stirring rate stirring of 250rpm at 170 DEG C in closed container.Then, products therefrom is made It filters out and is washed with deionized for solid, until the conductivity of washing water reaches the value lower than 150 μ S.Then, solid is existed It is 12 hours dry at 90 DEG C in air.Then, solid is heated to 90 DEG C in air with 3.5 DEG C/min of the rate of heat addition, Then it is kept for 2 hours at said temperatures.Then, solid is heated to 120 DEG C with 1.5 DEG C/min of the rate of heat addition, then existed It is kept for 2 hours at the temperature.Then, solid with 4.5 DEG C/min of the rate of heat addition is heated to 550 DEG C and in the temperature It is lower to be kept for 12 hours.Yield is 82g.
According to elemental analysis, the every 100g substance of products therefrom measures content with following: < 0.1g carbon, 4.9g aluminium, 3.2g sodium With 37g silicon.
Measuring BET surface area is 404m2/g.The crystallinity for measuring product is 90%.
Can be seen that gained zeolitic material from the X-ray diffractogram of products therefrom shows MOR framework structure as monocrystalline Phase, wherein being determined as 59nm by the average crystalline size that X ray diffracting data calculates, the average crystalline size of 002 axis of crystallite is true It is set to 46nm.
Using 70g ammonium nitrate as aqueous solution (10 weight %NH4NO3) be placed in 2L agitating device, 70g zeolitic material is added, Gained mixture is stirred 2 hours at 80 DEG C.Then, it filters out zeolitic material and distills water washing with 630g.Filtrate is discarded, so The 10 new aqueous solutions of weight % comprising 70g ammonium nitrate are placed in agitating device afterwards, washed zeolitic material is added thereto, And gained mixture is stirred 2 hours at 80 DEG C again.Then, it filters out zeolitic material and is relaundered with 630g distilled water. Then, washed material is 5 hours dry at 120 DEG C, it is then calcined 5 hours at 500 DEG C, the rate of heat addition is 2 DEG C/minute Clock.Then entire program is repeated, to obtain the zeolitic material of the H-shaped formula of 63.4g.
According to elemental analysis, the every 100g substance of gained sample measures content with following: < 0.1g carbon, 5.0g aluminium, 0.01g Sodium and 38g silicon.
Measuring BET surface area is 474m2/g。
Embodiment 4: the synthesis of the modenite of copper exchange
In agitating device, 2.4kg pyrogenic silica (CAB-O-SIL M5, Sigma-Aldrich) is suspended in In 18kg deionized water.Into the suspension be added 1.04kg tetraethylammonium bromide (TEABr, Aldrich) in 1.04kg go from Solution in sub- water.Gained mixture is stirred 1 hour under the stirring rate of 150rpm.Then, 0.73kg hydroxide is added Solution of the sodium piece (NaOH, Sigma-Aldrich) in 3.5kg deionized water.Then, the stirring in 180rpm by gained mixture It mixes and is stirred 1.5 hours under rate.Then, 0.31kg sodium aluminate (NaAlO is added2, Sig-ma-Aldrich) and in 4kg deionized water In solution, and for wash include forma solution container 3kg deionized water.Then, gained mixture is existed It is stirred 1 hour under the stirring rate of 180rpm.The pH value for measuring gained gel is 13.1.Then, by gel aged overnight.
Then, it would indicate that mole group becomes 0.5Na2O:0.0475Al2O3:SiO2:44.5H2The conjunction of O:0.125TEABr Be heated to 170 DEG C under 200rpm stirring in closed container at gel, and 170 DEG C at this temperature with phase same rate into The stirring of one step is lower to be kept for 84 hours.Then, it would indicate that pH is that 12.5 products therefrom is filtered out as solid and gone respectively with 50L Ion water washing five times, until the conductivity of washing water reaches the value of 85 μ S.Then, filter cake is heated to 100 DEG C and by nitrogen Stream guidance is by filter cake up to 16 hours to dry at such a temperature.Thus to obtain 1.667kg crystalline material, then by it 550 It is calcined 12 hours at DEG C, thus to obtain 1.533kg white powder.
According to elemental analysis, the every 100g substance of products therefrom measures content with following: < 0.1g carbon, 5.3g aluminium, 3.2g sodium With 35g silicon.
Measuring BET surface area is 400m2/g.The crystallinity for measuring product is 93%.
The X-ray diffractogram of the products therefrom shown from Fig. 1 can be seen that gained zeolitic material and show MOR framework Structure is as monocrystalline phase.The average crystalline size of the crystallite calculated by X ray diffracting data is determined as 57.5nm.
Using 650g ammonium nitrate as solution (the 10 weight %NH in 5.85kg distilled water4NO3) it is placed in agitating device In, zeolitic material of the 650g through calcining is added into the solution, gained mixture is heated to 80 DEG C under stiring and in the temperature Degree is lower to be kept for 2 hours.Then zeolitic material is filtered out, filtrate is discarded, it is then that the 10 weight % comprising 650g ammonium nitrate are newly water-soluble Liquid is placed in agitating device, and the zeolitic material filtered out is added thereto, and gained mixture is stirred 2 hours at 80 DEG C again. Then, it filters out zeolitic material and distills water washing with 12L.Then, washed material is 5 hours dry at 120 DEG C, then It is calcined 5 hours at 500 DEG C, to obtain white powder.
According to elemental analysis, the every 100g substance of gained sample measures content with following: < 0.1g carbon, 5.4g aluminium, 0.1g sodium With 40g silicon.
Then, the 10 new aqueous solutions of weight % comprising 650g ammonium nitrate are placed in agitating device, and by the powder through calcining End is added in the solution, then gained mixture is heated to 80 DEG C under stiring and is kept for 2 hours at such a temperature.So Afterwards, it filters out zeolitic material and distills water washing with 12L.Then washed material is 5 hours dry at 120 DEG C, then exist It is calcined 5 hours at 500 DEG C, to obtain the zeolitic material of H-shaped formula.
According to elemental analysis, the every 100g substance of gained sample measures content with following: < 0.1g carbon, 5.0g aluminium, 0.01g Sodium and 38g silicon.
Measuring BET surface area is 438m2/g。
1.8L 0.01M copper acetate (II) aqueous solution (3.6g, in 1.8L) is placed in 2L agitating device, is then added Mixture is stirred at room temperature 20 hours the zeolitic material of 30g H-shaped formula.Then zeolitic material is filtered out, filtrate is discarded.So Afterwards, the new soln of 1.8L 0.01M copper acetate (II) aqueous solution (3.6g, in 1.8L) is placed in 2L agitating device, thereto Zeolitic material is added, mixture is stirred at room temperature 20 hours.Then zeolitic material is filtered out, discards filtrate, and by zeolite material Material is added in the new soln of 1.8L0.01M copper acetate (II) aqueous solution (3.6g, in 1.8L) again and is stirred at room temperature 20 hours.Then, products therefrom is separated by being centrifuged from solution, discards solution, zeolitic material is then suspended in 1.5L In distilled water.Then, zeolitic material is separated by being centrifuged from solution, discards washing water, and wash repeatedly journey with distilled water Sequence 3 times to wash zeolitic material.Then, zeolitic material is 24 hours dry at 110 DEG C, to obtain the boiling of 22g copper exchange Stone material.
According to elemental analysis, the every 100g substance of products therefrom measures content with following: 0.17g carbon, 4.4g aluminium, 2.6g copper With 36g silicon.
Measuring BET surface area is 425m2/g。
Embodiment 5: the synthesis of the modenite of copper exchange
Using 650g ammonium nitrate as solution (the 10 weight %NH in 5.85kg distilled water4NO3) it is placed in agitating device In, 650g is added into the solution and is handed in example 4 by crystallization acquisition and the non-copper ion after washing, drying and calcination The zeolitic material with MOR framework structure changed, and gained mixture is heated to 80 DEG C under stiring and is protected at such a temperature It holds 2 hours.Then zeolitic material is filtered out, filtrate is discarded, is then placed in the 10 new aqueous solutions of weight % comprising 650g ammonium nitrate In agitating device, the zeolitic material filtered out is added thereto and stirs gained mixture 2 hours at 80 DEG C again.Then, It filters out zeolitic material and distills water washing with 12L.Then washed material is 5 hours dry at 120 DEG C, then 500 It is calcined 5 hours at DEG C, to obtain white powder.
According to elemental analysis, the every 100g substance of gained sample measures content with following: < 0.1g carbon, 5.4g aluminium, 0.1g sodium With 40g silicon.
Then, the 10 new aqueous solutions of weight % comprising 650g ammonium nitrate are placed in agitating device, and by the powder through calcining End is added in solution, then gained mixture is heated to 80 DEG C under stiring and is kept for 2 hours at such a temperature.Then it filters Out zeolitic material and with 12L distill water washing.Then washed material is 5 hours dry at 120 DEG C, then at 500 DEG C Lower calcining 5 hours, to obtain the zeolitic material of H-shaped formula.
According to elemental analysis, the every 100g substance of gained sample measures content with following: 4.6g aluminium, 0.01g sodium and 38g Silicon.
Measuring BET surface area is 438m2/g。
The zeolitic material of 40g H-shaped formula and 7.85g copper acetate (II) are placed in laboratory grinder (Microton MB550 it in), and is ground 15 minutes under 4 grades, subsequent mixture reaches 30.1 DEG C of temperature (being measured by infrared thermometer).So Afterwards, gained mixture is placed in rotary calciner, is heated to 500 DEG C with 2 DEG C/min of rate, and at such a temperature in sky It is calcined 3 hours in gas.The program has obtained the zeolitic material of 32.9g Copper Ion Exchange.
According to elemental analysis, the every 100g substance of products therefrom measures content with following: < 0.1g carbon, 4.2g aluminium, 6.6g copper With 35g silicon.
Measuring BET surface area is 401m2/g。
Embodiment 6: the synthesis of the modenite of copper exchange
1.5L 0.01M copper acetate (II) aqueous solution (3g, in 1.5L) is placed in 2L agitating device, 25g is then added Mixture is stirred at room temperature 20 hours the product of embodiment 1.Then zeolitic material is filtered out, filtrate is discarded.Then, will The new soln of 1.5L 0.01M copper acetate (II) aqueous solution (3g, in 1.5L) is placed in 2L agitating device, and boiling is added thereto Mixture is stirred at room temperature 20 hours stone material.Then zeolitic material is filtered out, filtrate is discarded, zeolitic material is added again Enter into the new soln of 1.5L 0.01M copper acetate (II) aqueous solution (3g, in 1.5L), and is stirred at room temperature 20 hours.So Afterwards, products therefrom is separated by being centrifuged from solution, discards solution, then zeolitic material is suspended in 1.25L distilled water. Then, zeolitic material is separated by being centrifuged from solution, discards washing water, and wash repeatedly program 3 times with distilled water to wash Wash zeolitic material.Then, zeolitic material is 24 hours dry at 110 DEG C, thus obtain the zeolitic material of 24.4g copper exchange.
According to elemental analysis, the every 100g substance of products therefrom measures content with following: < 0.1g carbon, 4.8g aluminium, 2.6g copper With 35g silicon.
Measuring BET surface area is 371m2/g。
Embodiment 7: the synthesis of the modenite of zinc exchange
50g is obtained in example 4 and in washing, after drying and calcination and the H-shaped formula without Copper Ion Exchange Zeolitic material is placed in a beaker, and the water of 5.22g zinc acetate (II) dihydrate being dissolved in 50ml distilled water is added thereto Solution stirs gained mixture with scraper.Then zeolitic material is filtered out, filter cake is dry at 110 DEG C in drying oven 12 hours, then with 2 DEG C/min of rate be heated to 500 DEG C and at such a temperature calcine 5 hours, thus obtain 54.3g zinc from The zeolitic material of son exchange.
According to elemental analysis, the every 100g substance of products therefrom measures content with following: < 0.1g carbon, 4.1g aluminium, 2.9g zinc With 38g silicon.
Embodiment 8: the synthesis of copper and the modenite of zinc exchange
1.8L 0.01M copper acetate (II) aqueous solution (3.6g, in 1.8L) is placed in 2L agitating device, is then added The zeolitic material of the zinc ion exchange obtained in 30g embodiment 7, mixture is stirred at room temperature 20 hours.Then boiling is filtered out Stone material discards filtrate.Then the new soln of 1.8L 0.01M copper acetate (II) aqueous solution (3.6g, in 1.8L) is placed in 2L In agitating device, zeolitic material is added thereto, mixture is stirred at room temperature 20 hours.Then zeolitic material is filtered out, is abandoned Filtrate is gone, zeolitic material is added to the new soln of 1.8L 0.01M copper acetate (II) aqueous solution (3.6g, in 1.8L) again In, it is stirred at room temperature 20 hours.Then products therefrom is separated by centrifugation from solution, solution is discarded, then by zeolite Material is suspended in 1.5L distilled water.Then zeolitic material is separated by centrifugation from solution, discards washing water, and with distilling Water washes repeatedly program 3 times to wash zeolitic material.Then zeolitic material is 24 hours dry at 110 DEG C, thus obtain The zeolitic material of 20.4g copper and zinc exchange.
According to elemental analysis, the every 100g substance of products therefrom measures content with following: 0.11g carbon, 4.2g aluminium, 2.7g Copper, 35g silicon and 1.0g zinc.
Measuring BET surface area is 425m2/g。
Embodiment 9: H- modenite is synthesized by commercially available Na-MOR
The 200g ammonium chloride in 800ml distilled water is dissolved in as aqueous solution (20 weight %NH4Cl) it is placed in 2L stirring In device, it is added 100g Na- modenite (FM-8, Zeochem), gained mixture is stirred 2 hours at 100 DEG C.Then It filters out zeolitic material and is washed with distilled water, until washing water not chloride.Then washed material is done at 120 DEG C It dry 12 hours, is then calcined 5 hours at 500 DEG C, the rate of heat addition is 2 DEG C/min.The program has obtained 97.8g H-shaped formula Commercial zeolite material.
According to elemental analysis, the every 100g substance of gained sample measures content with following: < 0.1g carbon, 2.8g aluminium, < 0.01g Sodium and 38g silicon.
It is calculated by the X ray diffracting data of commercial samples, the average crystalline size along 002 axis of crystallite is determined as 77nm.
Embodiment 10: according to the synthesis of the UZM-14-B of US 7,687,423B2
91g pyrogenic silica (CAB-O-SIL M5, Sigma-Aldrich) is provided in 2L plastic beaker.In list In only plastic beaker, 960g deionized water is weighed, and 15.63g sodium hydroxide (NaOH, Sigma- are added under stiring Aldrich), 11.28g sodium aluminate (NaAlO2, Sigma-Aldrich) and 12.65g tetraethylammonium bromide (TEABr, Aldrich), mixture is futher stirred until realizing that it is completely dissolved.Then, solution is added to comprising heat under stiring To provide viscous gel in the beaker of solution silica, futher stirred 2 hours.Then, by thus obtained display Mole group becomes 0.2Na out2O:0.051Al2O3:SiO2:39.5H2Synthesized gel rubber (1.07kg) distribution of O:0.045TEABr exists In several closed containers, then crystallized 76 hours under the stirring of 300rpm stirring rate at 150 DEG C.Then, by products therefrom It filters out, be washed with deionized and dry as solid, be then that will be consolidated with 2 DEG C/min of the rate of heat addition in a nitrogen atmosphere The step of body is heated to 540 DEG C and calcines material at said temperatures 2 hours, then continues to forge in air at such a temperature It burns 5 hours.Yield is 59.1g.
According to elemental analysis, the every 100g substance of products therefrom measures content with following: < 0.1g carbon, 4.7g aluminium, 2.8g sodium With 38g silicon.
Measuring BET surface area is 416m2/g.The crystallinity for measuring product is 80%.
The X-ray diffractogram of the products therefrom shown from Fig. 1 can be seen that gained zeolitic material and show MOR framework Structure is as monocrystalline phase.The crystallinity for measuring product is 80%, is determined as by the average crystalline size that X ray diffracting data calculates 47.5nm。
The 50g ammonium nitrate in 450g distilled water is dissolved in as aqueous solution (10 weight %NH4NO3) it is placed in 2L stirring dress In setting, 50g zeolitic material is added, gained mixture is stirred 2 hours at 80 DEG C.Then, filter out zeolitic material and with distillation Water washing, until washing water is free of nitrate.Then, 10 weights of the 50g ammonium nitrate being dissolved in 450g distilled water will be included The amount new aqueous solution of % is placed in agitating device, washed zeolitic material is added thereto, by gained mixture again at 80 DEG C Lower stirring 2 hours.Then, it filters out zeolitic material and is relaundered with distilled water, until washing water is free of nitrate.It then will be through The material of washing is 4 hours dry at 120 DEG C, then calcines in air at 500 DEG C 5 hours.Then entire program is repeated, To obtain the zeolitic material of the H-shaped formula of 40.8g.
According to elemental analysis, the every 100g substance of gained sample measures content with following: 4.2g aluminium, < 0.01g sodium and 38g Silicon.
Measuring BET surface area is 486m2/g.The crystallinity for measuring product is 71%, is calculated by X ray diffracting data flat Equal crystalline size is determined as 47nm, and is determined as 33nm along the average crystalline size of 002 axis of crystallite.
Embodiment 11: commercially available NH4 +The modenite of exchange
By NH4 +The commercial samples of modenite (CBV 21A, Zeolyst) are calcined at 550 DEG C to obtain its H-shaped formula.
According to the technical data that supplier provides, the elemental analysis of commercial samples has 0.08g sodium (with every before being calcined The Na of 100g substance2O is calculated) and show 500m2The surface area of/g.
The commercially available modenite of embodiment 12:H form
Directly using commercial samples embodiment 12 as a comparison of H- modenite (TZM-1013, Tricat).
According to elemental analysis, the every 100g substance of sample, which has, following measures content: < 0.1g carbon, 5.4g aluminium, 0.03g sodium and 36g silicon.
It is calculated by the X ray diffracting data of commercial samples, average crystalline size is determined as 71nm, and along 002 axis of crystallite Average crystalline size be determined as 99nm.
The commercially available modenite of embodiment 13:H form
Directly using commercial samples embodiment 5 as a comparison of another H- modenite (MOR-1501, Novel).
According to elemental analysis, the every 100g substance of sample measures content with following: 5.1g aluminium and 40g silicon.
It is calculated by the X ray diffracting data of commercial samples, average crystalline size is determined as 91.5nm, along 002 axis of crystallite Average crystalline size is determined as 83nm.
Embodiment 14: commercial zeolite Y
Directly using commercial samples (CBV 600, Zeolyst) embodiment 2 as a comparison of zeolite Y.
According to the technical data that supplier provides, the elemental analysis of sample has 0.2g sodium (with the Na of every 100g substance2O Calculate) and show 660m2The surface area of/g.
Embodiment 15: the synthesis of the zeolitic material with GME and CHA framework types
In teflon beaker, by 74.38g NaAlO2Under stiring in 832.64g waterglass (26 weight %SiO2, 8 weights Measure %Na2O, 66 weight %H2O homogenizing in).This results in milk white gels, add 8.02g chabasie seed (3.7 weights wherein % is measured, SiO is based on2).Therefore, gained reaction gel shows SiO2:Al2O3:Na2O:H2O molar ratio is 40.3:3.5:12.0: 705.Reaction mixture is transferred in the autoclave of stirring and is heated 60 hours to 120 DEG C.Then dispersion is cooling, pass through Solid and supernatant separation are then used H by filtering2O (DI) washing is until reach the conductivity of 200 μ S.It is residual in order to completely remove The H stayed2O dries sample 16 hours in air at 120 DEG C in static oven.Obtain 121g white powder.
By X-ray diffraction measure, product is shown as in addition to the phase with GME skeleton structure, mainly has CHA skeleton The zeolitic material of structure.The phase of the GME and CHA skeleton structure in zeolitic material measured using relative intensity ratio (RIR) method It is 93%CHA and 7%GME to amount.It is 71% by the product crystallinity that diffraction pattern determines.
The 4.8g ammonium nitrate in 43.2g distilled water is dissolved in as aqueous solution (10 weight %NH4NO3) it is placed in stirring dress In setting, 4.8g zeolitic material is added, gained mixture is stirred 2 hours at 80 DEG C.Then zeolitic material is filtered out, it then will packet The 10 new aqueous solutions of weight % containing the 4.8g ammonium nitrate being dissolved in 43.2g distilled water are placed in agitating device, are added thereto The zeolitic material filtered out stirs gained mixture 2 hours at 80 DEG C again.Then, it filters out zeolitic material and is steamed with 600ml Distilled water washing, until washing water is free of nitrate.Then washed material is 5 hours dry at 120 DEG C, then 500 It is calcined in air at DEG C 5 hours.Then entire program is repeated, to obtain the zeolitic material of the H-shaped formula of 3.4g.
According to elemental analysis, the every 100g substance of sample measures content with following: 10.0g aluminium, < 0.03g calcium, 0.02g potassium, 0.16g sodium and 34g silicon.
Comparative example 1: the synthesis of the zeolitic material with CAN framework types
1.35kg distilled water is placed in a beaker, 432g sodium hydroxide and molten under the cooling beaker of ice water is added thereto Solution.15g kaolinite (Fluka) and 51g sodium bicarbonate are added into solution, then stirs 30 minutes, it is solidifying thus to obtain 1.846kg Glue.
Then, synthesized gel rubber is heated to 200 DEG C under 100rpm stirring in closed container, and with phase same rate into It is kept at such a temperature 48 hours under the stirring of one step.Then, it filters out and washs using products therefrom as solid, until washing water base It is no longer conductive in sheet.Then filter cake is dried 24 hours in air at 80 DEG C, to obtain the reddish brown toner of 4.4g End.
The crystallinity for measuring product is 97%.
It can be seen that gained zeolitic material from the X-ray diffractogram of products therefrom and show CAN skeleton structure, wherein by X The average crystalline size that ray diffraction data calculates is determined as 119nm.
The 5g ammonium nitrate in 45g distilled water is dissolved in as aqueous solution (10 weight %NH4NO3) be placed in agitating device, 4.4g zeolitic material is added, and gained mixture is stirred 2 hours at 80 DEG C.Then zeolitic material is filtered out, then will include The 10 new aqueous solutions of weight % of the 5g ammonium nitrate being dissolved in 45g distilled water are placed in agitating device, and addition filters out thereto Zeolitic material stirs gained mixture 2 hours at 80 DEG C again.Then, it filters out zeolitic material and is washed with distilled water, directly Nitrate is free of to washing water.Then washed material is 4 hours dry at 120 DEG C, then at 500 DEG C in air Calcining 5 hours.Then entire program is repeated, to obtain the zeolitic material of the H-shaped formula of 3.5g.
Embodiment 16: catalyst test
In the carrier gas stream being made of nitrogen and specific quantity methane (as internal standard), make hydrogen, ammonia and monoethylene glycol (MEG) it is evaporated at a certain temperature according to its partial pressure.Ammonia evaporates in the first evaporator, and MEG is in second evaporator in downstream Middle evaporation.Then gained gas vapor stream is heated to 200 DEG C.
Zeolitic material to be tested is mixed with the graphite of 3 weight % respectively, and by shaking and mixing homogenizing, if needed If wanting, mortar and pestle are used.Then using the granulation tool that diameter is 13mm by the mixture pelleting of homogenizing, wherein basis Zeolite applies the power of 10-40kN, so that stable pellet and therefore stable target fraction are obtained, wherein the height of gained pellet Degree is 2-3mm, diameter 13mm.Then, thus obtained pellet mortar and pestle are crushed in advance, and passes through 1000 μm Analysis sieve screening.It repeats to crush and sieve to obtain the required mesh that partial size is 315-500 μm using suitable analysis sieve and pestle Fraction is marked, and wherein removes particulate (< 315 by sieving on screening media (such as Retsch AS 200) or sieving manually μm)。
The gas vapor stream is fed and is filled with 1cm3In reactor having a size of 315-500 μm of catalyst granules.It urges The diameter of agent bed is 4mm, length 80mm.It is isothermal since the diameter of catalyst bed is small.Catalyst bed it Before, by making gas vapor stream that gas vapor stream are heated to reaction temperature by inert bed.Catalyst bed and inert bed are all Reaction temperature is heated in outside.In the downstream of catalyst bed, by product diluted stream and it is cooled to 250 DEG C.Further downstream, pass through Online GC measures its composition.
Pass through the phase for obtaining the ratio of educt and internal standard (IS) with the gas vapor stream by analysis from bypass pipe Carry out calculated result with ratio reference.Therefore undetected product (high-boiling components, coke) is had also contemplated.It is given below detailed Program:
Conversion ratio: X (educt)=1-c (educt)/c (IS)/(c (educt _ bypass)/c (IS- bypass))
Yield: Y (product)=c (product)/c (IS)/(c (educt _ bypass)/c (IS- bypass))
Selectivity: S (product)=Y (product)/X (educt)
For standard test, select following test condition: gas hourly space velocity (GHSV) is 5000h-1, MEG concentration is 1 body Product %.In addition to main educt MEG, gas streams are by 40 volume % ammonia, 20 volume % hydrogen and as interior 1 volume % first of target Alkane and as surplus nitrogen form.Catalyst is heated to 300-340 DEG C of reaction temperature in nitrogen, then by gas Charging switches to test condition.By implementing existing as the result is shown for catalysis test acquisition on embodiment 1-15 and comparative example 1 In the following table 1, wherein the yield of ethylenediamine and the conversion ratio of MEG are indicated respectively with %, and also show the list generated in reaction The amount (%) of ethanol amine (MEOA) and piperazine (PIP).About by embodiment 4 and 6 obtain as a result, described value is respectively indicated by 2 The value that a different round obtains.
Table 1: the Catalytic test results of embodiment 1-15 and comparative example 1
The average-size of (*) 002 crystal face is less than 55nm
The average-size of (* *) 002 crystal face is greater than 55nm
Therefore, the result shown from table 1 can be seen that comprising the zeolite with MOR, FAU, CHA or GME framework types All samples of the present invention of material, at obvious excellent performance is all shown in EDA, either turn with regard to MEG in MEG Study on Catalytic Amination of Alcohols For rate, for the EDA yield still achieved that.The result obtained from embodiment 6 is compared with the result that embodiment 3 obtains As can be seen that increasing although carrying out ion exchange to H-shaped formula with copper and will lead to MEG conversion ratio, EDA yield can drop slightly It is low.The result obtained from embodiment 5 is compared with the result that embodiment 3 obtains as can be seen that the increase of copper load capacity not will lead to As a result improve.
However, the result shown from table 1 can be seen that all present invention of the zeolitic material with MOR framework structure Sample all has the 002 crystal face average-size (referring to embodiment 3,6 and 10) less than 55nm, in MEG Study on Catalytic Amination of Alcohols in EDA Show obvious excellent performance, either for MEG conversion ratio, for the EDA yield still achieved that, especially with The sample of zeolitic material with MOR framework structure of the 002 crystal face average-size less than 55nm is compared.
By test sample acquisition as a result, it is further noted that being obtained using the zeolitic material with MOR type skeleton structure Highest EDA yield and MEG conversion ratio.With the comparative example 1 for using the zeolitic material with CAN type skeleton structure to implement It compares, although being shown using the test round that the zeolitic material in embodiment 14 with FAU type skeleton structure is implemented slightly worse MEG conversion ratio, however the EDA yield obtained in embodiments of the present invention is high more than twice.On the other hand, have about having used The combined embodiment 15 of the zeolitic material of CHA type skeleton structure and the zeolitic material with GME type skeleton structure, although with right It is compared than embodiment 1, which give slightly worse EDA yields, however are almost to the MEG conversion ratio that the embodiment of the present invention is observed 4 times of height.
Therefore, as previously described, in fact it has surprisingly been found that the zeolitic material with MOR, FAU, CHA or GME skeleton structure, it is special It is not that there is the zeolitic material of MOR framework structure significant improved catalytic activity, Er Qiejin are not only shown in the amination of MEG One step shows that the selectivity that height improves, the result of this EDA yield that can be obtained from sample of the present invention are observed.Therefore, non- Often it was unexpectedly found that, by using the zeolitic material with MOR, FAU, CHA or GME skeleton structure, especially with tool There is the zeolitic material of MOR framework structure, can get the method by MEG amination at EDA being highly improved.
The existing technical literature list of reference:
-WO 2014/135662A
-US 7,605,295
-US 7,687,423B2
- Grundner, Sebastian etc., Nat.Commun.2015, volume 6, document number 7546
-US 4,918,233
-CN 1962058A
-JP H0687797A
-JP H07247245A
-CN 101215239B
-CN 101406845A
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Thesis " Heterogeneous Transition Metal Catalyzed Amination of Aliphatic Diols ", Achim Fischer, Diss.ETH No 12978,1998
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Claims (15)

1. a kind of convert ethane -1,2- diamines and/or formula H for ethane -1,2- glycol2N-[CH2CH2NH]n-CH2CH2NH2Line The method of property polyethyleneimine, wherein n >=1, which comprises
(i) it provides comprising containing YO2And X2O3Zeolitic material catalyst, wherein Y be quadrivalent element, X is triad, wherein The zeolitic material is selected from the zeolitic material with MOR, FAU, CHA and/or GME skeleton structure, including its two or more Combination；
(ii) gas streams comprising the pure and mild ammonia of ethane -1,2- two are provided；
(iii) contact the catalyst provided in (i) with the gas streams provided in (ii), so that ethane -1,2- glycol be turned Turn to ethane -1,2- diamines and/or L-PEI.
2. the method according to claim 1, wherein the gas streams packet for providing in (ii) and being contacted in (iii) with catalyst Containing the ethane -1,2- glycol in an amount of from 0.1-10 volume %.
3. method according to claim 1 or 2, wherein the gas material for providing in (ii) and being contacted in (iii) with catalyst Stream includes the ammonia in an amount of from 5-90 volume %.
4. method as claimed in one of claims 1-3, wherein providing in (ii) and being contacted in (iii) with catalyst Gas streams further include the hydrogen in an amount of from 0.1-70 volume %.
5. method as claimed in one of claims 1-4, wherein providing in (ii) and being contacted in (iii) with catalyst Gas streams include in an amount of from 5 volume % or less H2O。
6. method as claimed in one of claims 1-5, wherein the gas streams provided in (ii) are heated to 120-600 DEG C Temperature, then contacted at such a temperature with catalyst in (iii).
7. method as claimed in one of claims 1-6, wherein Y be selected from Si, Sn, Ti, Zr, Ge and its two or more Mixture.
8. method as claimed in one of claims 1-7, wherein X is selected from Al, B, In, Ga and its mixing of two or more Object.
9. method according to claim 1 to 8, wherein the H-shaped formula of the zeolitic material and include that proton is made It is calculated based on the element and wherein 0.1 weight % or the outer ion of less skeleton are metal cation based on boiling for ion outside skeleton 100 weight %YO contained in stone material2。
10. method according to claim 1 to 9, wherein the zeolitic material is substantially free of Na.
11. method as claimed in one of claims 1-10, wherein the zeolitic material with MOR framework structure is along crystallite 002 The average particle size of axis is 5 ± 1nm to 55 ± 8nm, is measured by powder x-ray diffraction.
12. any one of -11 method according to claim 1, wherein the catalyst provided in (i) includes to have MOR framework knot The zeolitic material of structure.
13. any one of -12 method according to claim 1, wherein the zeolitic material with MOR framework structure by include with It is prepared by the method for lower step:
(1) preparation includes at least one YO2Source, at least one X2O3Source, and include one or more having as structure directing agent Machine template and/or mixture comprising crystal seed；
(2) make the crystalline mixture prepared in (i), to obtain the zeolitic material with MOR framework structure；
(3) it is optionally separated the zeolitic material obtained in (2)；
(4) zeolitic material optionally obtained in washing (2) or (3)；
(5) zeolitic material that is optionally dry and/or calcining acquisition in (2), (3) or (4)；
(6) ion exchange procedure optionally is implemented to the zeolitic material obtained in (2), (3), (4) or (5), wherein zeolitic material Contained in the outer ion of skeleton and H+Carry out ion exchange；
(7) ion exchange procedure optionally is implemented to the zeolitic material obtained in (2), (3), (4), (5) or (6), wherein zeolite The outer ion of skeleton contained in material and one or more metal ions Ms selected from alkaline-earth metal and/or transition metal carry out from Son exchange；
(8) zeolitic material that is optionally dry and/or calcining acquisition in (7).
14. method according to claim 13, wherein the step of making zeolitic material be subjected to ion exchange procedure in (6) include with Lower step:
(6.a) implements ion exchange procedure to the zeolitic material obtained in (2), (3), (4) or (5), wherein institute in zeolitic material The outer ion of the skeleton contained and NH4+Carry out ion exchange；
(6.b) calcines the zeolitic material through ion exchange obtained in (6.a), to obtain the zeolitic material of H-shaped formula.
15. any one of -14 method according to claim 1, wherein by second contained in the gas streams obtained in (iii) Alkane -1,2- glycol and/or 2- ethylaminoethanol separate from the gas streams and are recycled to (ii).
CN201780070277.3A 2016-11-30 2017-11-29 Using zeolite catalyst by the ethylene glycol reforming method for ethylenediamine Pending CN109996781A (en)

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